Engineering Chemistry

MRCETCAMPUS
MALLAREDDYCOLLEGEOFENGINEERING&TECHNOLOGY
(AUTONOMOUSINSTITUTION-UGC,GOVT.OFINDIA)
AffiliatedtoJNTUH;ApprovedbyAICTE,NBA-Tier1&NAACwithA-GRADEIISO9001:2015
Maisammaguda,Dhulapally,Komaplly,Secunderabad-500100,TelanganaState,India
DIGITALNOTES
ENGINEERING CHEMISTRY
.
2024-25(R24)
COURSE STRUCTURE B.TECH: I YEAR R24
MALLA REDDY COLLEGE OF ENGINEERING ANDTECHNOLOGY

I Year B. TECH –I/II SEM L/T/P/D C
3/ -/ - / 3
COURSE OBJECTIVES: The students will be able
1. To analyze water for its various parameters for sustainable living and interpret different problems
involved in industrial utilization of water.
2. To acquire the knowledge on fundamental aspects of battery chemistry, significance of corrosion and
it’s control to protect the metallic structures.
3. To identify different types of polymers and their applications in various engineering fields.
4. To understand the basic concepts of fuels and its products.
5. To gain knowledge on wide variety of engineering materials like composite materials, smart
materialsand lubricants which have excellent engineering properties.
Unit –I Water and its treatment: (8 hours)

Introduction – hardness of water – causes of hardness; Types of hardness - temporary and permanent –
expression and units of hardness-numerical problems on hardness; Potable water and its specifications -
Steps involved in the treatment of potable water-Disinfection of potable water by chlorination and break
- point chlorination.
Boiler troubles: Sludges, Scales and Caustic embrittlement. Internal treatment of Boiler feed water -
Calgon conditioning - Phosphate conditioning, External treatment methods - Softening of water by ion-
exchange process. Desalination of water – Reverse osmosis.
UNIT–II Battery Chemistry & Corrosion: (8 hours)

Introduction - Classification of batteries-primary, secondary and reserve batteries with examples. Basic
requirements for commercial batteries. Construction and working of Lithium ion battery, Applications of
Li-ion battery to electrical vehicles. Fuel Cells- Differences between battery and a fuel cell, Construction
and applications of Methanol Oxygen fuel cell. Solar cells - Introduction and applications of Solar cells.
Corrosion: Causes and effects of corrosion – theories of chemical (oxidation) and electrochemical
corrosion – mechanism of electrochemical corrosion, Types of corrosion: Galvanic, waterline and pitting
corrosion. Factors affecting rate of corrosion- nature of metal (position, passivity, purity, relative areas of
anode and cathode); nature of environment (temperature, pH and humidity); Corrosion control methods-
Cathodic protection –Sacrificial anode and impressed current methods.
UNIT-III: Polymeric materials: (8 hours)

Definition–Classification of polymers based on source with examples–Types of polymerization–
characteristics of addition and condensation polymerization with examples.
Plastics: Definition and characteristics-thermoplastic and thermosetting plastics, Preparation, Properties
and engineering applications of PVC, Teflon and Bakelite.
Fibers: preparation, properties and applications of Nylon 6,6.
Rubbers: Natural rubber and its vulcanization.
Conducting polymers: Characteristics and Classification with examples-mechanism of conduction in trans-
polyacetylene and applications of conducting polymers.
Biodegradable polymers: Concept and advantages – preparation, properties of Polylactic acid and
its applications.
Malla Reddy College of Engineering and Technology www.mrcet.ac.in

COURSE STRUCTURE B.TECH: I YEAR R24
UNIT-IV: Energy Sources: (8 hours)

Introduction- Calorific value of fuel – HCV and LCV. Classification- solid fuels: coal – analysis of coal –
proximate and ultimate analysis and their significance. Liquid fuels – petroleum and its refining, cracking
types – moving bed catalytic cracking. Knocking – octane and cetane rating, synthetic petrol - Fischer-
Tropsch’s process; Gaseous fuels – composition and uses of natural gas, LPG and CNG.
Unit- V Engineering Materials: (8 hours)

Composite materials: Introduction-Fiber reinforced plastics (FRPs) - Glass fiber reinforced plastics, Carbon
fiber reinforced plastics and their applications.
Smart materials and their engineering applications
Shape memory materials – Poly L – Lactic acid. Thermo-responsive materials- Poly acryl amides, Poly vinyl
amides.
Lubricants: Classification of lubricants with examples-characteristics of a good lubricant - properties of
lubricants- definition and significance of viscosity, cloud and pour point, flash and fire point.
Suggested Text Books:

1. Engineering Chemistry by P.C. Jain & M. Jain: Dhanpat Rai Publishing Company (P) Ltd, New Delhi.
16th Edition, 2010.
2. Engineering Chemistry by Prasanta Rath, B. Rama Devi, C. H. Venkata Ramana Reddy, Subhendu
Chakroborty, Cengage Learning Publication, India Private Limited, 2018.
3. Engineering Analysis of Smart Material Systems by Donald J. Leo, Wiley, 2007.
Reference Books:
1. Engineering Chemistry by Shashi Chawla, Dhanpat Rai Publishing Company (P) Ltd, New Delhi.
2. Engineering Chemistry, by S. S. Dara, S. Chand & Company Ltd, New Delhi.
3. P.W. Atkins, J.D. Paula, “Physical Chemistry”, Oxford, 8thedition (2006).
4. B.R. Puri, L.R. Sharma and M.S. Pathania, “Principles of Physical Chemistry”, S. Nagin Chand &
Company Ltd., 46th edition (2013).
COURSE OUTCOMES: At the end of the course the student is expected to know the fundamental
principles of Engineering Chemistry required solving engineering problems.
The students will be able

1. To identify water as an engineering material and develop innovative methods to produce soft water
forindustrial use and potable water at cheaper cost.
2. To relate the knowledge of operating principles of batteries and different corrosion control
techniques for sustainable development.
3. To recognize the significance of polymeric compounds in various engineering applications and
biodegradable polymers to reduce environmental pollution.
4. To analyze the importance of various energy resources in day today life.
5. To interpret the role of engineering materials for technological improvements in various sectors.
Malla Reddy College of Engineering and Technology www.mrcet.ac.in

S. No. Contents Page No.

Unit-I: Water and its treatment
1 Introduction – hardness of water – causes of hardness 1
2 Expression and units of hardness-numerical problems on hardness 2
3 Types of hardness - temporary and permanent 3
Potable water and its specifications - Steps involved in the treatment of 5
4
potable water
Disinfection of potable water by chlorination and break - point 8
5
chlorination
6 Boiler troubles: Sludges, Scales and Caustic embrittlement 9
Internal treatment of Boiler feed water - Calgon conditioning - Phosphate 13
7
conditioning
8 External treatment methods - Softening of water by ion- exchange process 14
9 Desalination of water – Reverse osmosis 16
UNIT-II: Battery Chemistry & Corrosion
Introduction - Classification of batteries-primary, secondary and reserve 18
10
batteries with examples
Basic requirements for commercial batteries. Construction and working 19
11 of Lithium-ion battery, Applications of Li-ion battery to electrical
vehicles
Fuel Cells- Differences between battery and a fuel cell, Construction and 23
12
applications of Methanol Oxygen fuel cell
13 Solar cells - Introduction and applications of Solar cells 26
Corrosion: Causes and effects of corrosion – theories of chemical 29
14
(oxidation)
15 Electrochemical corrosion – mechanism of electrochemical corrosion 32
16 Types of corrosion: Galvanic, waterline and pitting corrosion 34
Factors affecting rate of corrosion- nature of metal (position, passivity, 37
17 purity, relative areas of anode and cathode); nature of environment
(temperature, pH and humidity)
Corrosion control methods- Cathodic protection –Sacrificial anode and 38
18
impressed current methods
UNIT-III: Polymeric materials
19 Definition–Classification of polymers based on source with examples 40
Types of polymerization– characteristics of addition and condensation 41
20
polymerization with examples
Plastics: Definition and characteristics-thermoplastic and thermosetting 42
21
plastics
Preparation, Properties and engineering applications of PVC, Teflon and 44
22
Bakelite
23 Fibers: preparation, properties and applications of Nylon 6, 6. 46
24 Rubbers: Natural rubber and its vulcanization. 47
Conducting polymers: Characteristics and Classification with examples- 49
25 mechanism of conduction in trans-polyacetylene and applications of
conducting polymers
Biodegradable polymers: Concept and advantages – preparation, 50
26
properties of Polylactic acid and its applications
DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

UNIT-IV: Energy Sources

27 Introduction- Calorific value of fuel – HCV and LCV 52
Classification- solid fuels: coal – analysis of coal –proximate and ultimate 54
28
analysis and their significance
29 Liquid fuels – petroleum and its refining 61
30 Cracking types – moving bed catalytic cracking 63
31 Knocking – octane and cetane rating 65
32 Synthetic petrol - Fischer-Tropsch’s process 68
33 Gaseous fuels – composition and uses of natural gas, LPG and CNG 69
Unit-V: Engineering Materials
34 Composite materials: Introduction 70
Fiber reinforced plastics (FRPs) - Glass fiber reinforced plastics, Carbon 71
35
fiber reinforced plastics and their applications
36 Smart materials and their engineering applications 73
37 Thermo-responsive materials- Poly acryl amides, Poly vinyl amides 74
38 Shape memory materials – Poly L – Lactic acid 77
39 Lubricants: Classification of lubricants with examples 78
40 Characteristics of a good lubricant - properties oflubricants 80
definition and significance of viscosity, cloud and pour point, flash and fire 81
41
point
DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

Introduction:
Like air water is one of the few basic materials which is of prime importance for the
preservation of life on this earth. All are aware of the uses of water for drinking, cooking,
bathing and farming etc., but few know the importance of water as an engineering material.
For the existence of all living beings (humans, animals and plants) water is very crucial.
Without water we cannot survive and almost all human activities–domestic, agricultural and
industrial demand use of water. Although water is nature’s most wonderful and abundant
compound but only less than 1% of the world’s water resources are available for ready use.
As engineering material water is used for producing steam in boilers to generate hydroelectric
power, furnishing steam for engines, for refrigeration and air conditioning, for construction of
concrete structures for manufacturing purposes and as a solvent in the chemical process.
Hardness:
The hardness of water is defined as the property which prevents the lathering of soap.
This is due to the presence of certain salts of Ca+2, Mg+2 and other heavy metals dissolved in
it. Soaps are sodium or potassium salts of higher fatty acids like oleic acid or palmitic acid or
stearic acids (C17H35COONa). Hard water does not give lather with soap while soft water
gives lather readily with soap.
Soap with hard water reactions:
When soap comes in contact with soft water lather is produced due to sodium stearate.
C17H35COONa + H2O → C17H35COOH + NaOH
(Sodium stearate) (Stearic acid)
When soap comes in contact with hard water, sodium stearate will react with dissolved
calcium and magnesium salts and produce calcium stearate or magnesium stearate which is
white precipitate. This insoluble white precipitate prevents lathering of soap.
2C17H35COONa + CaCl2 → (C17H35COO)2 Ca + 2NaCl
(Sodium stearate) (insoluble scum)
2C17H35COONa + MgSO4 → (C17H35COO)2 Mg + Na2SO4
(Sodium stearate) (insoluble scum)
Different types of water have different degrees of hardness. The different types of water are
commercially classified on the basis of degree of hardness as follows:
Hardness Name of water
0-70mg/liter Soft water
70-150mg/liter Moderate hard water
150-300mg/liter Hard water
300mg/liter and above Very hard water
DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 1

Degree of hardness:
The total hardness of water is caused by eight different dissolved salts of calcium and
magnesium, [Ca(HCO3)2, Mg(HCO3)2, CaCl2, MgCl2, CaSO4, MgSO4, Ca(NO3)2 and
Mg(NO3)2]. Hence the hardness of water is expressed in terms of calcium carbonate
equivalents. The weight of different hardness salts causing hardness are converted to weight
equivalent to that of calcium carbonate. CaCO3 is selected for expression of hardness because
the molecular weight of CaCO3 is 100, which is easy for calculation and it is the most
insoluble salt and all the dissolved salts of calcium are precipitated as CaCO3.
Name of the salt Molecular weight
Ca(HCO3)2 162
Mg(HCO3)2 146
CaCl2 111
MgCl2 95
CaSO4 136
MgSo4 120
CaCO3 100
The method for calculating degree of hardness will be clear from the following formula:
Hardness of water in terms of calcium carbonate equivalents
Amount of hardness causing salts
= 100
Molecular weight of hardness causing salts
Causes of hardness:
Natural water is usually contaminated by different types of impurities.
They are mainly 3 types
1. Physical impurities
2. Chemical impurities
3. Biological impurities
4. Collodial impurities
Expression of hardness – Units

Units of Hardness:
1Parts Per Million: Parts of CaCO3 equivalent hardness per 106 parts of water.
1 ppm = 1 part of CaCO3 equivalent hardness present in 106 parts of water.
Milligram per liter: Number of milligrams of calcium carbonate equivalent hardness present
in 1 liter of water.
1mg / L = 1 mg of CaCO3 equivalent hardness present in 1 liter of water.

1 L = 1 Kg = 1000 g = 1000 x 1000 mg = 106 mg.

1mg /L= 1 mg of CaCO3eq per 106 mg of H2O = 1ppm
Degree Clark: (°Cl): It is the number of grains (1/7000 lb) of CaCO3 equivalent hardness
per 70,000 parts of water.
1Clark = 1 grain of CaCO3 equivalent hardness per gallon of water.
= 1 part of CaCO3 of hardness per 70,000 parts of water.
Degree French (°Fr): It is the parts of CaCO3 equivalent hardness per 105 parts of water.
10French =1 part of CaCO3 per 105 parts of hard water
Milliequivalents per litre : - No of milliequivalents of hardness present per liter of water.

1m eq/L= 1 m eq of CaCO3 per / liter of water = 50 mg /L of CaCO3eq = 50ppm
Relation between various units of hardness:
1 ppm = 1mg /L = 0.10Fr = 0.07 0Cl = 0.02 meq /L
Total hardness of the sample water=121ppm=121mg/L

121x0.07=8.47ocl and 121x0.1=12.1oFr
Permanent hardness=101mg/l,101ppm,7.07ocl,10.1oFr
Temporary hardness=20mg/l,20ppm, 1.4ocl and 20Fr
Types of Hardness:
Hardness of water is mainly two types
1. Temporary Hardness
2. Permanent Hardness
1. Temporary Hardness:
It is caused mainly due to the presence of dissolved bicarbonates of calcium,
magnesium and other heavy metals. The salts mainly responsible for temporary hardness of
water are Calcium bicarbonate Ca(HCO3)2 and Magnesium bicarbonate Mg(HCO3)2 .
When bicarbonates are decomposed, yielding insoluble carbonates or hydroxides, which gets
deposited as a crust at the bottom of vessel. Temporary hardness can be largely removed by
mere boiling of water. On boiling bicarbonates converts into corresponding carbonates which
are insoluble. They can be removed by filtration.
Ca(HCO3)2 → CaCO3 + H2O + CO2

(Calcium bicarbonate)
Mg(HCO3)2 → Mg(OH)2 + 2CO2

(Magnesium bicarbonate)

2. Permanent Hardness:
It is due to the presence of dissolved chlorides and sulphates of calcium, magnesium,
iron and other metals. The salts responsible for permanent hardness are CaCl2, MgCl2,
CaSO4, MgSO4, FeSO4, Al2(SO4)3. Permanent hardness cannot be removed by boiling but it
can be removed using chemical agents.
Total hardness of water =Temporary hardness+Permanent hardness
Hardness-Numerical Problems:
1) One liter of water from an underground reservoir in Nalgonda town in Andhra Pradesh
found to have the fallowing dissolved salts. Mg(HCO3)2=14.6mg, NaCl=11.7mg.
MgCl2=48mg, CaSO4=13.6mg, Ca(HCo3)2=32.4mg. Find the total hardness temporary
&permanent hardness of water in degree French.
Solution:
S.No Salt Amount (mg) Multiplication CaCO3
factor equivalents
1 Mg(HCO3)2 14.6 100/146 14.6x100/146

=10
2 NaCl 11.7 ------ -----------------
3 MgCl2 48 100/95 48x100/95 =50
4 CaSO4 13.6 100/136 13.6x100/136

=10
5 Ca(HCO3)2 32.4 100/162 32.4x100/162

=20
Temporary hardness = Mg(HCO3)2+ Ca(HCO3)2

= 10 + 20 = 30 ppm
Permanent hardness = CaSO4 + MgCl2
= 10 + 50 = 60 ppm
Total Hardness = Temporary hardness + Permanent hardness = 30 + 60 = 90 ppm
In degree French = 90×0.07 = 6.3oFr

2) One liter of water from Khammam Dist. in Andhra Pradesh showed the following
analysis: Mg(HCO3)2 = 0.0256gms, Ca(HCO3)2 = 0.0156gms, NaCl = 0.0167gms, CaSO4
= 0.0065gms, and MgSO4 = 0.0054gms. Calculate temporary, permanent and total
hardness.
Solution:
S.No Salt Amount (mgs) Multiplication CaCO3 equivalents
factor
1 Mg(HCO3)2 25.6 100/146 25.6x100/146=17.5
2 Ca(HCO3)2 15.6 100/162 15.6x100/162 =9.6
3 NaCl 16.7 ------------- --------------
4 CaSO4 6.5 100/136 6.5x100/136 =4.77
5 MgSO4 5.4 100/120 5.4x100/120 =4.5
Temporary hardness = Mg (HCO3)2 + Ca (HCO3)2

= 17.5 + 9.6 = 27.1ppm
Permanent hardness = CaSO4+ MgSO4
= 4.77 + 4.5 = 9.27ppm
Total Hardness = Temporary hardness + Permanent hardness
= 27.1 + 9.27 =36.37ppm
POTABLE WATER:
Drinking water or potable water is safe enough to be consumed by humans or used
with low risk of immediate or long-term harm. In most developed countries the water
supplied to households, commercial and industry needs drinking water standards, even
though only a very small proportion is consumed or used in food preparation. As water flows
over the surface of earth it picks up several impurities in the form of dissolved particles of
soil, garbage, pesticides and other human, animal or chemical wastes. Some of these
impurities may make water more useful and potable and some of these renders it harmful and
unfit.
Drinking or potable water, fit for human consumption, should satisfy the following essential
requirements:
1. It should be sparkling clear and odour less.
2. It should be pleasant in taste.
3. It should be perfectly cool.
4. Its turbidity should not exceed 10ppm.
5. It should be free from objectionable dissolved gases like hydrogen sulphide.
6. It should be free from minerals such as lead, arsenic, chromium and manganese salts.
7. Its alkalinity should not be high.
8. Its pH should be about 8.0.
9. It should be reasonably soft.

10. Its total dissolved solids should be less than 500 ppm.
11. It should be free from disease-producing micro-organisms.
12.Chloride, fluoride and sulphide contents should be less than 250ppm, 1.5ppm and 250ppm
respectively.
Steps involved in treatment of potable water:
Screening:
To protect the main units of a treatment
plant and to aid in their efficient
operation, it is necessary to use screens to
remove any large floating and suspended
solids that are present in the inflow. These
materials include leaves, twigs, paper,
rags and other debris that could obstruct
flow through the plant or damage
equipment. There are coarse and fine
screens
Aeration:
After screening, the water is aerated (supplied with air) by passing it over a series of steps so
that it takes in oxygen from the air. This helps expel soluble gases such as carbon dioxide and
hydrogen sulphide (both of which are acidic, so this process makes the water less corrosive)
and expels any gaseous organic compounds that might give an undesirable taste to the water.
Aeration also removes iron or manganese by oxidation of these substances to their insoluble
form. Iron and manganese can cause peculiar tastes and can stain clothing. Once in their
insoluble forms, these substances can be removed by filtration.
Coagulation and flocculation:
After aeration, coagulation takes place, to remove the fine particles (less than 1 µm in size)
that are suspended in the water. In this process, a chemical called a coagulant (with a positive
electrical charge) is added to the water, and this neutralises the negative electrical charge of

the fine particles. The addition of the coagulant takes place in a rapid mix tank where the
coagulant is rapidly dispersed by a high-speed impeller (Figure)
The next step is flocculation. Here the water is gently stirred by paddles in a flocculation
basin (Figure) and the flocs meet each other to form larger flocs.
The flocculation basin often has several compartments with decreasing mixing speeds as the
water advances through the basin (Figure). This compartmentalised chamber allows
increasingly large flocs to form without being broken apart by the mixing blades. Chemicals
called flocculants can be added to enhance the process. Organic polymers called
polyelectrolytes can be used as flocculants.
Sedimentation
Once large flocs are formed, they need to be settled
out, and this takes place in a process
called sedimentation (when the particles fall to the
floor of a settling tank). The water (after coagulation
and flocculation) is kept in the tank (Figure 5.6(b))
for several hours for sedimentation to take place.
The material accumulated at the bottom of the tank
is called sludge; this is removed for disposal.
Filtration
Filtration is the process where solids are separated from a liquid. In water treatment, the
solids that are not separated out in the sedimentation tank are removed by passing the water
through beds of sand and gravel. Rapid gravity filters (Figure), with a flow rate of 4–8 cubic
metres per square metre of filter surface per hour are often used.

Disinfection of surface water / Removal of micro-organisms in water:

Disinfection:
The process of destroying/killing the disease producing Bacteria, microorganisms, etc. from
the water and making it safe for use, is called disinfection.
Disinfectants:
The chemicals or substances which are added to water for killing the bacteria are called
disinfectants.
The disinfection of water can be carried out by following methods:
a) Boiling:
When water is boiled for 10-15 minutes, all the disease-producing bacteria are killed, and
water becomes safe for use.
b) Bleaching power:
Bleaching powder contains 80% chlorine. When bleaching powder is mixed with water, the
result of chemical reaction produces a powerful germicide called hypochlorous acid. The
presence of chlorine in the bleaching powder produces disinfecting action, kills germs and
purifies the drinking water effectively.
CaOCl2 + H2O Ca(OH)2 + Cl2
H 2O + Cl2 HCl + HOCl
c) Chlorine:
Chlorination is the process of purifying drinking water by producing a powerful germicide
like hypochlorous acid. When this chlorine is mixed with water it produces hypochlorous
acid which kills the germs present in water.
H2O + Cl2 HOCl + HCl
Chlorine is a basic (means pH value is more than 7) disinfectant and is much effective over
the germs. Hence chlorine is widely used all over the world as a powerful disinfectant. A
chlorinator is an apparatus, which is used to purify water by chlorination process.
Break point chlorination:

The amount of chlorine required to kill bacteria and to remove organic matter is called break
point chlorination.
A typical relationship between the amount of chlorine added to water and the experimentally
determined free residual chlorine is shown in the graph below which explains the break point
chlorination.
(i) First (between points 1 and 2), the water reacts with reducing compounds in the water,
such as hydrogen sulfide. These compounds use up the chlorine, producing no chlorine
residual.

(ii) Between points 2 and 3, the chlorine reacts with organics and ammonia naturally found in
the water and forms chloro-organics and chloramines.
(iii) Between points 3 and 4, the added chlorine will break down most of the chloramines in
the water, leaving behind free chlorine which destroys pathogenic bacteria, lowering the
chlorine residual.
(iv) Finally, the water reaches the breakpoint, at point 4 (minima). The breakpoint is the point
at which the chlorine demand has been totally satisfied - the chlorine has reacted with all
reducing agents, organics, ammonia and pathogenic bacteria in the water. After minima
when more chlorine is added, it is not used in any reaction. Thus, the residual chlorine
keeps on increasing in proportion to added chlorine. Hence for effective killing of
microorganisms, enough chlorine must be added. Addition of chlorine in such dosages is
known as break point chlorination.
Advantages of breakpoint chlorination:

1. It ensures complete destruction of organic compounds which impart colour, bad odour
and unpleasant taste to water.
2. It destroys all the disease producing bacteria.
3. It prevents the growth of any weeds in water.
Boiler Troubles:
Water finds a great use in various industries for generation of steam in boilers. When
water is continuously evaporated to generate steam, the concentration of the dissolved salts
increases progressively causing bad effects for steam boilers. The boiler troubles that arise
are
1. Scale formation
2. Sludges formation
3. Caustic embrittlement

Scale and Sludge formation in boilers:

Boilers are employed for the generation of steam in power plants, where water is
continuously heated to produce steam. As more and more water is removed from water in the
form of steam, the boiler water gets concentrated with dissolved salts progressively reaches
the saturation point. At this point the dissolved salts are precipitated out and slowly settle on
the inner walls of the boiler plate. The precipitation takes place two ways
i) Sludge ii) Scale
Sludge:
Sludges are soft, loose and slimy precipitate formed within the boiler. It is formed at
comparatively colder portions of the boiler and collects in the area where the flow rate is
slow.
Reasons:
The dissolved salts whose solubility is more in hot water and less in cold water produce
sludges Eg. MgCO3, MgCl2, CaCl2, MgSO4. The sludges were formed at comparatively
colder portions of the boiler and get collected where rate of flow of water is low.
Dis-advantages:
a. Excessive sludge formation leads to settling of sludge in slow circulation area such as pipe
connections, plug openings, guage-glass connections leading to the choking of the pipes .
b. As the sludges are poor conductors of heat they cause loss of heat.
c. The working of the boiler is disturbed because of chocking of pipes by the sludge.
Prevention:
a. By using well softened water.
b. By blow down operation i.e. by drawing off a portion of concentrated water frequently.
Scales:
Scales are hard, adhering precipitates formed on the inner walls of the boilers. They
stick very firmly to the inner wall surface.
Sludges and Scales in boilers

Causes of scale formation:

Following are the causes:
a. Decomposition of calcium bicarbonate:
Ca(HCO3)2 → CaCO3 + H2O + CO2

In low pressure boilers, CaCO3 causes scale formation.
In high pressure boilers, CaCO3 becomes soluble.
CaCO3 +H2O → Ca(OH)2 + CO2
b. Decomposition of calcium sulphate:

Caso4 is more soluble in cold water, hence its solubility decreases as the temperature of the
boiler increases and precipitates out to produce hard scale on the surface of the bolier. The
solubility of Caso4 is 3200 ppm at 15Oc, reduces to 27 ppm at 320Oc and completely insoluble
in super-heated water in high pressure boilers. This is the main reason for the formation of
scales in high pressure boilers. CaSO4 scale is very hard, highly adherent and difficult to
remove
c. Hydrolysis of Magnesium salts:
Dissolved Magnesium salts undergo hydrolysis forming Mg(OH)2 precipitate causing scales.
MgCl2 + 2H2O →Mg(OH)2 + 2HCl
d. Presence of Silica: Silica presents in small quantities deposits as silicates like CaSiO3 and
MgSiO3. These are very difficult to remove.
Disadvantages:
a. Wastage of fuel:
The scale formation causes decreases of heat transfer. As a result, over heating is required
this causes consumption of fuel.
b. Lowering of boiler safety:
The hot scale cracks because of expansion and water suddenly comes in contact with
overheated iron plates. This causes in formation of large amount of steam suddenly. This
results in high pressure, causing the boiler to burst.
c. Decrease in efficiency:
Deposition of scales in the valves and condensers of the boiler, choke them partially. This
results in a decrease in efficiency of the boiler.
d. Danger of explosion:
Because of the formation of the scales. the boiler plate faces higher temperature outside and
lesser temperature inside due to uneven heat transfer resulting the development cracks in the
layers of scales. Water passes through the crack and comes in contact with boiler plates
having high temperature. This causes formation of large amount of steam suddenly
developing sudden high pressure which causes explosion of the boiler.

Removal of scales:
1. Scales can be removed by applying thermal shocks
2. Using scrapers, wire brush etc. scales can be removed.
3. Using certain chemicals scales can be removed. For example using 5-10% HCl.
Calcium carbonate scales can be removed. Calcium sulphate scales can be removed
using EDTA solution.
4. By blow down operation the scale formation can be avoided.
Prevention of scales or softening of hard water:
a. External treatment: Efficient softening of water is to be carried out by
i) Lime-soda process (ii) Zeolite process (iii) ion-exchange process
b. Internal treatment: Suitable chemicals are added to the boiler water either to
precipitate or to convert the scale into sludge.
1. Colloidal conditioning
2. Phosphate conditioning
3. Carbonate conditioning
4. Aluminates conditioning
5. Calgon conditioning
S.No Sludges Scales

1 Sludges are soft, loose and slimmy Scales are hard deposits.
precipitate
2 Sludges are non-adherent deposits and Scales stick firmly to the
can be removed easily inner surface of boiler and are
very difficult.
Sludges are formed by substances like Scales are formed by
3 CaCl2 MgCl2, MgSO4, MgCO3 substances, like CaSO4,
Mg(OH)2 etc.
4 Formed at comparatively colder portions Generally formed at heated
of the boiler. portions of the boiler.
5 Decrease the efficiency of boiler but are Decrease the efficiency of

less dangerous boiler and chances of
explosions are also there.
6 Can be removed by blow-down Cannot be removed by blow-
down
Caustic embrittlement:
Caustic embrittlement is a term used for the appearance of cracks inside the boilers
particularly at those places which are under stress such as riveted joints due to the high
concentration of alkali leading to failure of the boiler.
Reasons: It is a type of boiler corrosion caused due to the presence of alkali-metal carbonates
and bicarbonates in feed water and the presence of sodium carbonate.
Na2CO3+ H2O →NaOH + CO2
This caustic water flows inside the boiler and causes some minute hair-cracks, by capillary
action. On evaporation of water, the dissolved caustic soda increases its concentration which

attacks the surrounding area, thereby dissolving iron of boiler as sodium ferroate (Na2FeO2).
This causes embrittlement of boiler parts such as bends, joints, rivets etc, due to which the
boiler fails. Caustic cracking can be explained by considering the following concentration
cell. The iron at plane surfaces surrounded by dilute NaOH becomes cathodic and the iron at
bends, joints and rivets surrounded by highly concentrated NaOH becomes anodic which
consequently gets corroded
Prevention:
 By maintaining the pH of water and neutralization of alkali.
 By using sodium phosphate as softening reagents instead of sodium carbonate in the
external treatment of boiler feed water.
 Caustic embrittlement can also be prevented by adding tannin or lignin or Sodium
sulphate which prevents the infiltration of caustic-soda solution blocking the hair-cracks.
Treatment of water:
Internal treatment:
Internal treatment of boiler water is carried out by adding proper chemicals to
precipitate the scale forming impurities in the form of sludge and to convert the scale forming
chemicals into compounds which will stay in dissolved form in water.
1. Calgon conditioning
2. Phosphate conditioning
1. Calgon conditioning: Involves in adding Calgon to boiler water. It prevents the scale and
sludge formation by forming soluble complex compound with CaSO4.
Calgon = Sodium hexametaphosphate = Na 2 [Na4 (PO3)6]

Na 2[Na4 (PO 3)6] 2Na+ + [Na4 (PO3)6]
2CaSO4 + [Na4 (PO3)6] → [Ca2 (PO3)6 ]-2+ 2Na2SO4
2. Phosphate conditioning: The addition of sodium phosphate in hard water reacts with the
hardness causing agents and gives calcium and magnesium phosphates which are soft and
non-adhere and can be removed easily by blow-down operation. In this way, scale formation
is removed in high-pressure boilers.
3CaCl2 + 2 Na3PO4 → Ca3(PO4)2 + 6NaCl
3MgCl2 +2Na3PO4→ Mg3(PO4)2 + 6NaCl
The calcium phosphate and magnesium phosphate complexes were removed by blow down
operation.
The three phosphates employed for conditioning are
1. NaH2PO4 –sodium dihydrogen phosphate (acidic)

2. Na2HPO4 –Di sodium hydrogen phosphate (weakly alkaline)

3. Na3PO4-Trisodium phosphate (alkaline)
Trisodium phosphate is the most preferred reagent because it not only form complex with
Ca+2 and Mg+2 ions, but also maintains the pH of water between 9-10, where the calcium and
magnesium ions undergo complexation.
External treatment:
The treatment given to water for the removal of hardness causing salts before it is
taken into the boiler is called external treatment or softening of water. In industry three main
external treatment methods employed for softening of water are.
1. Ion-Exchange process, 2. Zeolite Process
Ion exchange process or deionization process or demineralization process

Ion-exchange process includes the exchange of the cations and anions of the dissolved
salts with H+ and OH- respectively. For these two types of ion-exchangers are used, which are
insoluble, cross–linked long chain organic polymers with microporous structure. In de-
ionization process all the ions present in water are eliminated by using ion-exchange resins.
Basically, resins with acidic functional groups are capable of exchanging H+ ions with other
cations. Resins with basic functional groups can exchange OH- ions with other anions.
Resins are classified as

1. Cation Exchange Resins
2. Anion Exchange Resins
1. Cation Exchange Resins:

These are mainly styrene divinyl benzene co-polymers, which contain sulphonic or
carboxylic functional groups. They can exchange their hydrogen ions with cations present in
water.
2. Anion Exchange Resins:

Anion exchange resins are styrene-divinyl benzene or amine-formaldehyde
copolymers, which contains amino, quaternary ammonium or quaternary phosphonium or
tertiary sulphonium groups as an internal part of the resin matrix. These, after treatment with

dilute NaOH solution become capable of exchanging their OH- ions with anions present in
water.
Cation Exchange Resins
2RH+ + Ca+2 R2Ca+2 + 2H+

2RH+ + Mg+2 R2Mg+2 + 2H+ (RH+ = cation exchange resin)
Anion Exchange Resins
2R1OH + Cl-2 2R1Cl + 2OH-

2R1OH- + SO4-2 R12SO4-2 + 2OH-
2R1OH +CO3-2 R12CO3-2 +2OH-
Regeneration:
When cation exchanger loses capacity of producing H+ ions and anion exchanger loses
capacity of producing OH- ions, they are said to be exhausted. The exhausted cation
exchanger is regenerated by passing it through dilute sulphuric acid.
R2Ca+2 + 2H+  2RH+ + Ca+2
The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.
R21SO4-2 + 2OH-  2R1OH- + SO4-2

Merits of Ion-exchange process:

1. This process can be used to soften highly acidic or alkaline water.
2. It produces water of very low hardness (2ppm). So it is very good for treating water for
use in high-pressure boilers.
Demerits of Ion-exchange process:

1. The equipment is costly and more expensive chemicals are needed.
2. If water contains turbidity, the output of the process is reduced. The turbidity must be
below 10 ppm; else it must be removed by coagulation and filtration.
Desalination of Brackish water:

The process of removing common salt from the water is known as desalination. Water
containing high concentration of dissolved solids with peculiar salty or brackish taste is
called brackish water. Sea water is an example of brackish water as it contains about 3.5% of
dissolved salts.
Commonly used methods for the desalination of brackish water are:
1. Reverse Osmosis 2. Electrodialysis
Reverse Osmosis:
When two solutions of unequal concentrations are separated by a semi permeable
membrane, flow of solvent takes place from dilute to concentrated sides, due to osmosis. If,
however, a hydrostatic pressure more than osmotic pressure is applied on the concentrated
side, the solvent flow is reversed, i.e. solvent is forced to move from concentrated side to
dilute side across the membrane. This is the principle of reverse osmosis. This membrane
filtration is also called ‘super-filtration’ or ‘hyper – filtration. The membrane consists of very
thin films of cellulose acetate, affixed to either side of a perforated tube. However, more
recently superior membranes made of polymethacrylate and polyamide polymers have come
into use.
Method of purification: The reverse osmosis cell consists of a chamber fitted with a semi
permeable membrane, above which sea water / impure water is taken and a pressure of 15 to
40 kg/cm2 is applied on the sea water / impure water. The pure water is forced through the
semi-permeable membrane which is made of very thin films of cellulose acetate.

Advantages:
1. Reverse osmosis possesses a distinct advantage of removing ionic as well as non-ionic,
colloidal and high molecular weight organic matter.
2. It removes colloidal silica, which is not removed by demineralization.
3. The maintenance cost is almost entirely on the replacement of the semi permeable
membrane.
4. The lifetime of membrane is quite high, about 2 years.
5. The membrane can be replaced within a few minutes, thereby providing a nearly
uninterrupted water supply.
6. Due to low capital cost, simplicity, low operating cost and high reliability, the reverse
osmosis is gaining ground at present for converting sea water into drinking water and for
obtaining water for very high-pressure boilers.

Battery is an electrochemical cell or often several electrochemical cells connected in series

that can be used as a source of direct electric current at constant voltages. A device which
converts chemical energy to electrical energy is called battery cells, connected electrically in
series. Batteries are commercial electrochemical cells.
ADVANTAGES OF BATTERIES:
(1) Batteries act as a portable source of electrochemical energy.
(2) The portability of electronic equipment in the form of handsets has been made possible by
batteries.
(3) A variety of electronic gadgets have been made more useful and popular with the
introduction of rechargeable storage batteries having reliability, better shelf life and
tolerance to service.
(4) For all commercial applications, batteries are constructed for their service. For example,
batteries for automotives and aircraft, stand by batteries etc.
Classification of Batteries:
Batteries can be classified into three main categories: primary batteries, secondary batteries,
and reserve batteries. Each type has distinct characteristics and applications.
1. Primary Batteries (Non-rechargeable)
Primary batteries are designed for single-use and cannot be recharged. Once they are
depleted, they must be disposed of. They are commonly used in low-drain devices.
Examples:
- Alkaline Battery: Commonly used in household items like remote controls, flashlights, and
clocks.
- Lithium Battery: Found in small electronics such as cameras, calculators, and certain
medical devices.
- Silver Oxide Battery: Used in small devices like watches, calculators, and hearing aids.

2. Secondary Batteries (Rechargeable)
Secondary batteries can be recharged and used multiple times. They are typically used in
applications where frequent battery replacement would be inconvenient or costly.
Examples:
- Lead-Acid Battery: Used in automotive applications, uninterruptible power supplies
(UPS), and large-scale energy storage.
- Nickel-Cadmium (NiCd) Battery: Found in power tools, medical devices, and emergency
lighting.
- Lithium-Ion (Li-ion) Battery: Common in portable electronics like smartphones, laptops,
and electric vehicles.
- Lithium Polymer (LiPo) Battery: Used in high-performance applications such as drones,
RC vehicles, and some portable electronics.
3. Reserve Batteries
Reserve batteries are designed to be stored in an inactive state and activated when needed.
They are used in critical applications where long shelf life and immediate power availability
are required. Activation typically involves introducing an electrolyte to the cell or connecting
internal components.
Examples:
- Thermal Battery: Used in military applications, missile guidance systems, and aerospace
applications. Activated by heating, which melts an electrolyte to start the electrochemical
reaction.
- Water-Activated Battery: Used in life-saving equipment such as life jackets and buoys.
Activated by exposure to water.
- Gas-Activated Battery: Activated by the introduction of a gas (e.g., oxygen) to start the
electrochemical process.
This classification system helps in understanding the suitable applications and limitations of
different types of batteries, ensuring the right choice for specific needs.
Basic requirements of a commercial battery:

A useful battery should fulfill the following requirements
1. It should be lite and compact for easy transport.
2. It should have a long life both when it is being used and when it is not used.
3. The voltage of the battery should not vary appreciably during its use.
For a battery to be commercially viable, it must meet several basic requirements to ensure it
is practical, safe, and effective for consumer and industrial use. Here are the fundamental
requirements:
1. Energy Density
- High Energy Density: The battery should store a large amount of energy relative to its
weight and volume to ensure it is compact and lightweight.

2. Power Density
- High Power Density: The battery should be able to deliver high power output when
needed, which is crucial for applications requiring quick bursts of energy.
3. Cycle Life
- Long Cycle Life: The battery should withstand many charge and discharge cycles without
significant degradation in performance.
4. Safety
- Safety Features: The battery must incorporate safety mechanisms to prevent overheating,
overcharging, short circuits, and other hazards.
- Stable Chemistry: The chemical composition should be stable under a wide range of
conditions to minimize the risk of fire or explosion.
5. Cost-Effectiveness
- Affordable Production: The materials and manufacturing processes should be cost-
effective to keep the overall price of the battery competitive.
- Long Lifespan: A longer lifespan reduces the need for frequent replacements, making it
more economical over time.
6. Environmental Impact
- Low Environmental Impact: The battery should use materials that are abundant, non-
toxic, and recyclable to minimize environmental harm.
- Sustainable Disposal: There should be clear guidelines and systems for safe disposal or
recycling of the battery at the end of its life.
7. Efficiency
- High Efficiency: The battery should have minimal energy loss during charging and
discharging processes.
- Low Self-Discharge Rate: The battery should retain its charge over long periods when not
in use.
8. Temperature Range
- Wide Operating Temperature Range: The battery should perform reliably across a broad
range of temperatures to ensure versatility in different environments.
9. Maintenance
- Low Maintenance: The battery should require minimal maintenance throughout its
operational life.
10. Compatibility
- Compatibility with Devices: The battery should be designed to fit a variety of devices and
applications, ensuring it can be widely adopted.
11. Regulatory Compliance
- Compliance with Standards: The battery must meet all relevant safety, performance, and
environmental standards set by regulatory bodies.

Differences between Primary, Secondary and Fuel cells:

Primary cell Secondary cells Fuel Cell
It acts as a simple It acts as a galvanic cell while It acts as a simple galvanic
galvanic cell. discharging and electrolytic cell cell.
while charging.
Cell reaction is not Cell reaction can be reversed. Cell reaction is not
reversible. reversible
Cannot be recharged. Can be recharged Do not store energy
Can be used as long as Can be used again and again by Energy can be withdrawn
the materials are active in recharging the cell indefinitely as long as
their composition. outside supply of fuel is
maintained
E.g: E.g: E.g:
Leclanche or dry cell. 1. Lead storage cell 2. Nicol or H2-O2, CH3OH-O2
Zn/NH4Cl (20%), ZnCl2/ Nickel cadmium battery emf
MnO2/C. emf =1.5V. =1.4 Applications:
Applications: Applications: Electronic Space vehicles due to their
Radios, torches, calculators, electronic flash light weight and the bi
transistors, hearing aids. units & cordless electronic product H2O produced is a
shavers etc. valuable source of fresh
water for astronauts.
Lithium-ion batteries (or) Lithium-ion cells

Lithium-ion battery is a secondary battery. As in lithium cells, it does not contain metallic
lithium as anode. As the name suggests, the movement of lithium ions are responsible for
charging & discharging. Lithium-ion cells have the following three components.
1. A positive electrode (Layers of lithium-metal oxide) (cathode).

2. A negative electrode (Layers of porous carbon) (anode).
3. An electrolyte (Polymer gel) (separator)
Construction:
The positive electrode is typically made from a layer of chemical compound called lithium-
cobalt oxide (LiCoO2).
The negative electrode is made from layers of porous carbon (C) (graphite).
Both the electrodes are dipped in a polymer gel electrolyte (organic solvent) and separated
by a separator, which is a perforated plastic and allows the Li + ions to pass through.
Working
Charging Reaction:
During charging, Li+ ions flow from the positive electrode (LiCoO2) to the negative electrode
(graphite) through the electrolyte. Electrons also flow from the positive electrode to the
negative electrode. The electrons and Li+ ions combine at the negative electrode and deposit
there as Li.

LiCoO2 + C→ Li1-xCoO2 + CLix

Charging Mechanism
charger Discharging Mechanism
load
electrons
electrons
seperator Cathode
Anode seperator
Anode Cathode
C LiCoO2
graphite
Li+
Li+
Li+ Li+ Li+
Li + Li+ Li+
Li+
C Li+ LiCoO2
Li+ Li+ Li+
graphite
+
Li+ Li+ Li+
Li
Li+
+ + Li+ +
Li Li Li Li+ Li+
Electrolyte (gel polymer electrolyte) Electrolyte (gel polymer electrolyte)
Discharging Reaction:
During discharging, the Li+ ions flow back through the electrolyte form negative electrode to
the positive electrode. Electrons flow from the negative electrode to the positive
electrode. The Li+ ions and electrons combine at the positive electrode and deposit there as
Li.
Li1-xCoO2 + CLix → LiCoO2 + C
Advantages (or) Characteristics:

1. Lithium-ion batteries are high voltage and light weight batteries.
2. It is smaller in size.
3. It produces three times the voltage of Ni-Cd batteries.
4. It has none of the memory effects seen in Ni-Cd batteries.
Applications:
It is used in cell phone, note PC, portable LCD TV, semiconductor driven audio, etc.

Applications of Li-ion battery to electrical vehicles:

Lithium-Ion (Li-Ion) batteries have become the dominant energy storage technology for
electric vehicles (EVs) due to their high energy density, long cycle life, and efficiency. Here
are some key applications of Li-Ion batteries in EVs:
1. Energy Storage: Li-Ion batteries store the electrical energy that powers the electric motor,
enabling the vehicle to run without internal combustion engines.
2. Regenerative Braking: These batteries can capture, and store energy generated from
regenerative braking systems, which convert kinetic energy back into electrical energy during
braking.
3. Range Extension: High-capacity Li-Ion batteries allow for greater driving ranges, making
EVs more practical for long-distance travel.
4. Hybrid Vehicles: In plug-in hybrid electric vehicles (PHEVs), Li-Ion batteries work
alongside internal combustion engines, providing electric-only driving for short distances and
improving overall fuel efficiency.
5. Start-Stop Systems: In hybrid vehicles, Li-Ion batteries help in start-stop systems by

providing the necessary power to restart the engine quickly when the vehicle is idling.
6. Auxiliary Power: Li-Ion batteries power auxiliary systems in EVs, such as infotainment
systems, lighting, and air conditioning, without significantly draining the primary battery
used for propulsion.
7. Vehicle-to-Grid (V2G) Technology: Li-Ion batteries in EVs can be used in V2G systems,
allowing EVs to supply power back to the grid during peak demand times, thereby stabilizing
the electrical grid.
8. Performance: High-performance EVs use Li-Ion batteries to deliver quick acceleration

and maintain high speeds due to their ability to discharge large amounts of energy quickly.
The versatility and efficiency of Li-Ion batteries make them a cornerstone of modern electric
vehicle technology, driving advancements in the automotive industry towards more
sustainable and eco-friendly transportation options.
FUEL CELL
A fuel cell is an electrochemical device that converts the chemical energy of a fuel, typically
hydrogen, directly into electricity through a pair of redox reactions. Unlike traditional
combustion-based power generation, fuel cells generate electricity without burning fuel,
resulting in higher efficiency and lower emissions.

Key Components and Operation of a Fuel Cell:
1. Electrolyte: The core component that conducts ions but is impermeable to electrons.
Common types include proton exchange membrane (PEM) and solid oxide.
2. Anode: The negative electrode where the fuel (e.g., hydrogen) is oxidized, releasing
electrons and creating positive ions.
3. Cathode: The positive electrode where oxygen molecules gain electrons and react with the
positive ions to form water or another byproduct.
4. Catalyst: Usually platinum or another precious metal, it speeds up the reactions at the
electrodes without being consumed.
Fuel cells are used in various applications, including stationary power generation,
transportation (e.g., fuel cell vehicles), and portable power systems. Research and
development are ongoing to improve their efficiency, reduce costs, and overcome other
technical challenges.
Differences between Battery and a Fuel cell

S. No Battery Fuel Cell
1. A battery is a galvanic cell (or a series of A fuel cell is a galvanic cell that requires
galvanic cells) that contains all the a constant external supply of fuel and
reactants needed to produce electricity. oxygen to generate electricity.
2 They store chemical energy and generate They do not store chemical energy and
electricity using stored energy
generates current as long as supply of
fuel and oxygen is maintained.
3 Reactants are within the cell itself Reactants for chemical reaction are
supplied continuously.
4 Non rechargeable/Rechargeable Not rechargeable
5 It consists of limited number of reactants Needs a continuous supply of fuel and

and these reactants diminish with time oxygen from an external source
6 Less efficiency High efficiency
7 Supply energy for a limited period of Supply energy for a long period of time
time
8 Less expensive They are expensive
9 Examples: Li cells, Li-ion cell etc. H2-O2, and CH3OH-O2

METHANOL OXYGEN FUEL CELL

CONSTRUCTION
Methanol Oxygen Fuel Cell is made of two fuel electrodes. One consists of Ni-Plate coated
with catalyst Pt-block and other is similar Ni-plate coated with silver catalyst, both electrodes
are placed in 25% KOH and NaOH, and air is allowed to bubble on the surface of the silver
catalyst. Now 35CC of pure methanol is added and the fuel cell is activated. When the cell
operates the water vapour and the CO2 are liberated at around the electrodes.
At the Anode:
Methanol and water are oxidized to carbon dioxide, releasing protons and electrons.
At the Cathode:
Oxygen molecules are reduced by gaining electrons and protons to form water
Overall reaction:
Methanol and oxygen are converted into carbon dioxide and water, generating electricity in
this process.

Applications:
1. Portable Power:
- DMFCs are suitable for portable electronic devices like laptops, smartphones, and military
equipment due to their compact size and ease of refueling with liquid methanol.
2. Transportation:
- Used in prototype and experimental fuel cell vehicles, DMFCs offer the advantage of
liquid fuel, simplifying storage and refueling compared to gaseous hydrogen.
3. Backup Power:
- Suitable for providing backup power to telecommunications infrastructure, emergency
systems, and remote sensors where reliability and long duration are critical.
4. Marine and Aerial Drones:

- DMFCs are used in drones and unmanned aerial vehicles (UAVs) for extended operation
times due to the high energy density of methanol.
5. Stationary Power Generation:

- While less common than other types of fuel cells, DMFCs can be used for small-scale
stationary power applications, particularly where methanol is readily available.
Advantages:
1. Fuel Availability: Methanol is easier to store and transport than hydrogen and can be
produced from various renewable resources.
2. Energy Density: Higher energy density of liquid methanol compared to hydrogen gas.
3. Simplified Infrastructure: Less complex infrastructure requirements for refueling and
storage compared to hydrogen fuel cells.
Despite these challenges, ongoing research aims to improve the performance, durability, and
cost-effectiveness of DMFCs, enhancing their viability for various applications.
Solar Cells
Solar cells, also known as
photovoltaic cells, convert light
energy directly into electrical
energy using the photovoltaic
effect. They are a key component
in solar panels and are widely
used for generating renewable
energy.

Here’s a simple diagram to illustrate the basic structure of a solar cell:
|-----------------------------------------|
| |
| Anti-Reflective Coating |
| |
|-----------------------------------------|
| |
| N-Type Silicon |
| |
|-----------------------------------------| <--- P-N Junction
| |
| P-Type Silicon |
| |
|-----------------------------------------|
| |
| Metal Back Contact Layer |
| |
|-----------------------------------------|
Construction:
1. Anti-Reflective Coating:
- Reduces the reflection of sunlight, allowing more light to enter the cell.
2. N-Type Silicon:
- The top layer of the semiconductor material, doped with elements (like phosphorus) that
have more electrons (negative charge carriers).
3. P-Type Silicon:
- The bottom layer of the semiconductor material, doped with elements (like boron) that
have fewer electrons, creating "holes" (positive charge carriers).
4. P-N Junction:
- The boundary between the p-type and n-type silicon where the electric field is created,
essential for separating charge carriers and generating electric current.
5. Metal Back Contact Layer:
- A conductive layer at the bottom of the cell that collects and conducts electrons out of the
cell into the external circuit.
Working Principle:
- Sunlight hits the anti-reflective coating, allowing photons to enter the cell.
- Photons are absorbed by the silicon layers, exciting electrons and creating electron-hole
pairs.
- The electric field at the P-N junction separates the electrons and holes, pushing electrons
toward the n-type layer and holes toward the p-type layer.
- Electrons flow through the metal contacts to the external circuit, generating an electric
current.

Applications of Solar cells:
1. Residential and Commercial Power Generation:

- Solar panels installed on rooftops or in solar farms to provide electricity for homes and
businesses.
2. Portable Power:
- Used in portable solar chargers for electronic devices and off-grid power solutions.
3. Remote and Rural Electrification:

- Provides electricity to remote or rural areas where grid access is limited or nonexistent.
4. Space Applications:
- Powering satellites and space stations due to their reliability and ability to generate power
in space.
5. Street Lighting and Traffic Signals:

- Solar-powered streetlights and traffic signals for energy-efficient and sustainable urban
infrastructure.

Introduction:
Metals and alloys are used as fabrication or construction materials in engineering. If the
metals or alloy structures are not properly maintained, they deteriorate slowly by the action of
atmospheric gases, moisture and other chemicals. This phenomenon of destruction of metals
and alloys is known as corrosion.
The surface of almost all the metals begin to decay rapidly when exposed to atmospheric
gases, water or other reactive liquid medium.
Corrosion
 The process of decay of metal by environmental attack is known as corrosion.
 Metals undergo corrosion and convert to their oxides, hydroxides, carbonates, sulphides,
etc.
 Examples: -
 i) Rusting of iron – when iron is exposed to the atmospheric conditions, a layer of reddish
scale and powder of Fe3O4 is formed.
 ii) Formation of green film of basic carbonate- [CuCO3 + Cu(OH)2] on the surface of copper
when exposed to moist air containing CO2.
 The corrosion of metals is measured in the units of milli/inches/year or mm/year.
Corrosion-Oxidation
Metal Metallic Compound + Energy
Metallurgy-Reduction
Corrosion is an oxidation process, and it is the reverse of metal extraction.

Causes of corrosion:
1. The metals exist in nature in the form of their minerals or ores in stable combined forms
as oxides, chlorides, silicates, carbonates and sulphides.
2. During the extraction of metals, these ores are reduced to metallic state by supplying
considerable amounts of energy.
3. Hence the isolated pure metals are in more excited states than their corresponding ores.
4. So, metals have a natural tendency to go back to their combined state (minerals/ores).
5. When metal is exposed to atmospheric gases, moisture, liquids etc, the metal surface
reacts and forms more thermodynamically stable compounds.
Effects of corrosion:
1. Wastage of metal in the form of its compounds.
2. The valuable metallic properties like conductivity, malleability, ductility etc. are lost due
to corrosion.
3. Life span and efficiency of metallic parts of machinery and fabrications is reduced

Theories of corrosion:
1. Dry corrosion
2. Wet corrosion
Dry corrosion or Chemical corrosion: The direct chemical action of environment on the
surface of metal in absence of moisture is known as dry corrosion.
This type of corrosion occurs mainly through the direct chemical action of
atmospheric gases like O2, halogens, H2S, SO2, N2 or anhydrous inorganic liquid with the
metal surface.
Example: (i) Silver materials undergo chemical corrosion by Atmospheric H S gas.
2
(ii) Iron metal undergo chemical corrosion by HCl gas.
There are three types of chemical Corrosion:

1. Oxidation corrosion
2. Corrosion due to other gases
3. Liquid metal corrosion
Oxidation Corrosion:
Direct action of oxygen at low or high temperatures on the surface of metals in absence of
moisture is known as oxidation corrosion. Alkali metals and Alkaline earth metals are rapidly
oxidized at lower temperatures. At high temperature all metals are oxidized (except Ag, Au,
Pt).
Mechanism:
1) Oxidation takes place at the surface of the metal forming metal ions M2+
2) Oxygen is converted to oxide ion (O2-) due to the transfer of electrons from metal.
3) The overall reaction is of oxide ions react with the metal ions to form metal oxide films.
Reactions in oxidation corrosion
Mechanism: Initially the surface of metal undergoes oxidation, and the resulting metal oxide
scale forms a barrier which restricts further oxidation. The extent of corrosion depends upon
the nature of metal oxide.

The nature of the oxide formed: It plays an important role in further oxidation corrosion process.
Metal + oxygen metal oxide (corrosion product)
When the oxide film formed is:
(a) Stable metal oxide layer

A stable layer is fine grained in structure and can get adhered tightly to the parent metal surface.
Such a layer will be impervious in nature and hence behaves as protective coating, thereby
shielding the metal surface. Consequently, further oxidation corrosion is prevented.
E.g.: Al, Sn. Pb, Cu, etc. form stable oxide layers on the surface thus preventing further
oxidation.
Example:
Unstable metal oxide layer

The oxide layer formed decomposes back into metal and oxygen. Consequently, oxidation
corrosion is not possible in such cases.
Eg: Ag, Au and Pt do not undergo oxidation corrosion.
Metal oxide Metal + oxygen
(c) Volatile Metal oxide layer

The oxide layer formed is volatile in nature and evaporates as soon as it is formed.
Thereby leaving the underlying metal surface exposed for further attack. This causes rapid
continuous corrosion, leading to excessive corrosion eg: Mo- molybdenum forms volatile MoO3
layer.

(d) Porous Metal oxide layer

If the metal oxide layer is porous, the oxide layer formed has pores or cracks. In this
case the atmospheric oxygen penetrates through the pores or cracks and corrodes the
underlying metal surface. This causes continuous corrosion till conversion of metal into its
oxide is completed. Eg: Alkali and alkaline earth metals (Li, Na, K, Mg, Fe etc.)
Example:
Wet Corrosion or Electrochemical Corrosion

 The direct chemical action of environment on the surface of metal in presence of
conducting liquid with the formation of electrochemical cells.
 It a common type of corrosion which occurs usually in aqueous corrosive
environment
 Occurs when metal meets a conducting liquid.
 Formation of galvanic cell on the surface of metal generating anodic and cathodic
areas
 At anode oxidation takes place liberates electrons.
 Electrons at anode are transported to cathodic area where H + or O2 and H2O consumes
the electrons generating non-metallic ions like OH- or O2-
 Metallic (M+) and non-metallic (OH- or O2-) diffuse towards each other and results in
the formation of corrosion product in between the anodic and cathodic area.
Mechanism: Electrochemical corrosion involves flow of electrons between anode and

cathode. The anodic reaction involves dissolution of metal liberating free electrons.
The cathodic reaction consumes electrons with either evolution of hydrogen or absorption of
oxygen which depends on the nature of corrosive environment.

Wet corrosion takes place in two ways.

1. Evolution of Hydrogen
2. Absorption of Oxygen
Evolution of Hydrogen:
This type of corrosion occurs in acidic mediums.
Eg: Rusting of iron metal in acidic environment takes place in the following way:
At Anode dissolution of iron to ferrous ion takes place with the liberation of electrons
The electrons released at anode flow through the metal from anode to cathode, whereas H+
ions of acidic solution take up these electrons and eliminated as hydrogen gas.
This type of corrosion causes “displacement of hydrogen ions from the acidic solution by metal
ions.
In hydrogen evolution type corrosion, the anodic areas are large and cathodic areas are small.
Absorption of Oxygen:
 This type of corrosion takes place in basic or neutral medium in presence of oxygen.
 For example, rusting of iron in neutral or basic aqueous solution of electrolyte in presence
of atmospheric oxygen.
 Usually, the surface of iron is coated with a thin film of iron oxide.
 If the film develops cracks, anodic areas are created on the surface and the rest of the
metal surface acts as cathodes.
 It shows that anodic areas are small, and the cathodic areas are large.
The released electrons flow from anode to cathode through iron metal.

If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide and then
to hydrated ferric oxide which is known as rust.
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
4Fe(OH )2  O2  2H2O 

oxidation
4Fe(OH )3 
oxidation
 Fe2O3.3H2O
Rust (hydrated ferric oxide)
The product called rust corresponds to Fe2O3.3H2O.
Types of Corrosion:
Galvanic Corrosion:
 When two dissimilar metals are electrically connected and exposed to an electrolyte, the
metal higher in electrochemical series (low reduction potential) undergoes corrosion and
the metal lower in electrochemical series (high reduction potential) is protected. This type
of corrosion is called galvanic corrosion.
 Eg: When Zn and Cu are connected and exposed to corroding environment, Zinc higher
in electrochemical series forms anode, undergoes oxidation and gets corroded. Cu lower
in electrochemical series acts as cathode, undergoes reduction and protected as the
electrons released by Zn flow towards Cu.

Examples of Galvanic corrosion

 Steel pipe connected to copper plumbing
 A steel propeller shaft in bronze bearing
 Lead antimony solder around copper wire
 Steel screws in a brass marine hardware
Galvanic corrosion can be minimized:

 By avoiding galvanic couple (contact of two dissimilar metals must be avoided
 By providing an insulating material between the two metals
Waterline corrosion or Differential Aeration Corrosion

This is the most common type of electrochemical corrosion that takes place when the metal is
partially dipped in solutions, metals partially covered with dust, sand, water drops etc. The
less aerated part acts as anode and the more aerated part acts as cathode. The anodic part
undergoes corrosion, and the cathodic part is prevented. This type of corrosion is called
Concentration Cell Corrosion.
Example: 1
When a metal is partially immersed in a solution it has very poor aeration when
compared with the metal that is outside the solution.
The less aerated part acts as anode and the more aerated part acts as cathode.
At anode: Corrosion occurs (less aerated) M M 2+ + 2e-

At cathode: OH- ions are produced (more aerated) ½ O 2 + H2O + 2e- 2OH-

Example: 2
Another example of this type of corrosion is the metal parts partially covered with dust, sand,
water drops etc. This type of corrosion is called pitting corrosion.
Pitting Corrosion
Pitting is a localized attack, resulting in the formation of a hole around which the
metal is relatively unattached.
Cathode
Fig Pitting Corrosion
The area covered by the drop of water acts as an anode due to less oxygen concentration and
suffers corrosion. The uncovered area (freely exposed to air) acts as a cathode due to high
oxygen concentration. The rate of corrosion will be more, when the area of cathode is larger,
and the area of anode is smaller.
2+
At anode : Fe Fe + 2e (Oxidation)
At cathode : ½O2 + H2O + 2e 2OH
Overall
[O]
Fe + ½ O2 + H2O Fe2+ + 2OH- Fe(OH)2 Fe(OH)3
This type of intense corrosion is called pitting.
Example: 3
This type of corrosion is also taking place in wire fence. In this case the areas where
the wires cross is less aerated than the other parts of the fence. The corrosion takes place at
the wire crossings because less aerated part act as anode.
Cathode
Cathode Anode Cathode
Cathode
Fig. 3.8 : Corrosion on wire fence

Factors effecting corrosion:

The rate and extent of corrosion depends on
1. Nature of Metal
2. Nature of Environment
Nature of metal:
1. Purity of the metal:
If impurities are present in a metal the corrosion rate is increased due to formation of tiny
electrochemical cells at the exposed parts and the anodic parts get corroded. Pure metal is
more corrosion resistant than impure metal. By increasing its purity, the corrosion resistance
of a metal can be improved
Ex: Zn metal containing impurity undergoes corrosion of zinc, due to the formation of
electrochemical cells. The rate and extent of corrosion increases with the increasing exposure
and extent of impurities.
2. Position of metal in galvanic series: Metals which possess low reduction potentials and
occupy higher end of galvanic series undergo corrosion easily.
Metals which possess high reduction potential and occupy lower end of galvanic series do not
undergo corrosion and they get protected.
 When two metals are in electrical contact in presence of an electrolyte, then the metal
which is more active undergoes corrosion.
 The rate of corrosion depends on the difference in their position in galvanic series.
The greater the difference will be the extent of corrosion at anode.
Eg: The potential difference between Fe and Cu is 0.78V which is more than that between Fe
and Sn (0.30V). Therefore, Fe corrodes faster when in contact with Cu than that with Sn. On
this account, the use of dissimilar metals should be avoided wherever possible (Eg. Bolt &
nuts, screw & washer).
3. Relative areas of anodic and cathodic parts: If the metal has small anodic and large
cathodic area, the rate of corrosion is very high. This is because the more electrons are
liberated at smaller anodic area, which are consumed at cathode. If the cathodic area is
larger, the liberated electrons are rapidly consumed at cathode. This further enhances the
anodic reaction leading to an increase in the rate of corrosion.
When two dissimilar metals or alloys are in contact,
corrosion at anodic area
4. Passivity:
A chemically inactive state used especially of a metal that has lost its normal chemical
activity and it is resistant to corrosion is known as passivity.

Nature of Environment:
1. Temperature: The rate of corrosion increases with increase in temperature due to increase
in diffusion rate.
Rate of corrosion α temperature
2. Humidity in air: The rate of corrosion increases with the presence of moisture in
atmosphere because the moisture or humidity present in atmosphere furnishes water to the
electrolyte which is essential for setting up of an electrochemical cell. The oxide film formed
has the tendency to absorb moisture which creates another electrochemical cell.
Rate of corrosion α Humidity
3. Effect of PH: pH value of the medium has the greater effect on corrosion. Generally acidic
medium (i.e. pH ) is more corrosive than basic medium. Acidic pH increases the rate of
corrosion. However, some metals like Al, Pbetc dissolve in alkaline solutions as complex
ions. Consequently, corrosion of metals, readily attacked by acid can be reduced by
increasing the PH of the attacking environment.
Acidic medium: PH - Corrosion is more

H
Basic medium: P - Corrosion is less
Eg: Zn which is readily corroded in acidic solutions suffers very less corrosion in alkaline
medium, i.e PH=11. Al has less corrosion at pH=5.5 which corrodes rapidly at PH= 8.5.
Corrosion control methods:

1. Proper designing
2. Using Pure metals
3. Using metal alloys
4. Use of inhibitors
5. Modifying Environment
6. Cathodic protection
7. Application of protective coatings
Cathodic Protection:
The method of protecting the base metal by forcibly making it behave like a cathode there by
corrosion does not occur is called cathodic protection.
There are two types of cathodic protection
(a) Sacrificial anodic protection
(b) Impressed current cathodic protection
Sacrificial anodic protection
 In this protection method, the metallic structure to be protected (base metal) is connected
by a conducting wire to a more anodic metal so that all the corrosion is concentrated at
this more anodic metal.
 The more anodic metal itself gets corroded slowly, while the parent structure (cathodic) is
protected. The more active metal so employed is called sacrificial anode. The corroded
sacrificial anode is replaced by a fresh one, when consumed completely.

 The artificially made anode thus gets corroded gradually protecting the original metallic
structure. Hence the process is known as sacrificial anodic protection.
 Metals commonly employed as sacrificial anode are Mg, Zn, Al and their alloys which
possess low reduction potential and occupies higher end in electrochemical series.
Eg: A ship-hull which is made up of steel is connected to sacrificial anode (Zn-blocks) which
undergoes corrosion leaving the base metal protected.
Unprotecte
d
Figure1. Sacrificial anode method: Ship hull and underground water pipeline
Ground Level
Soil Mg Sacrificial anode

Mg
Base Metal Iron

(underground pipe line)
Buried pipe line protected to Mg block
Applications of Sacrificial anodic protection:

By referring to the electrochemical series, the metal with low reduction potential is connected
to the base metal which acts as anode.
1. To protect underground pipelines- Buried pipeline protected by connecting to Mg block
2. Protection of ship hulls and other marine devices.
3. Protection of water tank- by suspending Zn or Mg rods, body of the tank made cathode
and protected.
Advantages:
1. It is a simple method.
2. It does not require external power.
3. It has low maintenance and installation cost
4. Cathodic interferences are minimum.
Disadvantages:
1. More than one anode is required sometimes.
2. It does not work properly in a highly corrosive environment.
3. Sacrificial anode must be replaced periodically as and when it is consumed.

Impressed current cathodic protection:

 In this method, an impressed current is applied in opposite direction to nullify the
corrosion current and convert the corroding metal from anode to cathode.
 The impressed current is slightly higher than the corrosion current. Thus, the anodic
corroding metal becomes cathodic and protected from corrosion.
 The impressed current is taken from a battery or rectifier on the A.C. line.
 The metal to be protected is made cathode by connecting to an external battery (-ve
terminal)
 The anode is usually an insoluble anode like graphite, stainless steel, or platinum
connected to +ve terminal of the battery. Usually a sufficient D.C current is passed on to
the insoluble anode kept in a black fill composed of coke or gypsum, to increase the
electrical contact with the surrounding soil.
 In impressed current cathodic protection, electrons are supplied from an external cell, so
that the object itself becomes cathodic and does not get oxidized.
_
Rectifier +
Ground Level
Soil
. .. . . .
.
.. . ... Anode
.. .
. .. . .. ...
(Graphite)
Burried pipe
made cathode . . Black fill
(protected) (gypsum)
Applications:
1. The impressive current cathodic protection is used for the protection of water tanks, water
& oil pipelines, transmission line towers etc.
Advantages
The method is mainly employed to protect large structures for long term operations.
Disadvantages
1. The method is expensive as it requires high current
2. Capital investment and maintenance costs are more
3. It is difficult to maintain uniform current over the entire metal surface as a result
localized corrosion may occur.
4. The metal should not be over protected, i.e., use of much high potential is avoided
otherwise problems related to cathodic reactions like evolution of H2 and formation of
OH- Ions talks place leading to corrosion of base metal

Polymers
Introduction:
Polymers form very important components in our daily life. Polymers are highly
useful in domestic, industrial & medical fields. The following are the reasons for the
extensive use of polymers.
1) Most of the polymers are non-toxic & safe to use
2) They have low densities (light in weight), so transportation of polymers will be easy
3) They possess good mechanical strength
4) They are resistant to corrosion and will not absorb moisture when exposed to the
atmosphere
5) They can function as good thermal & electrical insulators
6) They can be molded and fabricated easily
7) They possess esthetic colors
But the limitations for the use of polymers are:

 Some polymers are combustible.
 The properties of polymers are time dependent
 Some of them cannot withstand high temperatures.
 It is also interesting to note that many carbohydrates, proteins & enzymes, DNA &
RNA are natural polymers.
Polymer:
Polymers can be defined as the large molecules (macro molecules) formed by the linking
together of large number of smaller molecules called monomers. (In Greek language ‘poly’
means “many” & ‘mer’ means “units”)
E.g.: - polyethylene is a polymer formed by linking together of a large number of ethylene
molecules
Polymerization
nCH2 CH2 ( CH2 CH2 ) n
Thus, the repeated unit of polymer is called monomer. The number of repeating units in a
polymer chain is called degree of polymerization. For e.g. if 100 molecules of ethylene
polymerize to give the polymer chain, the degree of polymerization is 100.
Classification of polymers:
Classification based on source:
a) Natural polymers, which are found in nature. For example, starch, cellulose, proteins etc..
b) Synthetic polymers, which are man-made. For example, PVC, Teflon, Bakelite etc…

Types of polymerizations:
There are three types of polymerizations.
Chain Growth Polymerization: (Addition Polymerization)

Chain polymerization is a reaction that yields a polymer product which is the exact
multiple of monomers. Thus, the mechanism is also called addition polymerization. The
following are the characteristics.
1) The functionality of the monomer is a double bond, and it is bi-functional.

2) Polymerization takes place by self-addition of the monomer molecules to each other
through a chain reaction.
3) No biproducts like H2O, CH3OH etc. are produced.
4) The polymer has the same chemical composition as that of monomer.
5) The mechanism is carried out in three steps, i.e. initiation, propagation and termination.
6) The mechanism is rapid.
7) The conversion of Π bond to bond takes place during the polymerization, liberating 20
k.cal/mole of energy. Hence a highly exothermic reaction.
8) An initiator is required to start the polymerization reaction.
Step Polymerization (Condensation Polymerization)

Step polymerization takes place by condensation reaction of the functional groups of the
monomer, with the elimination of biproducts like H2O, HCl etc, hence known as
condensation polymerization. The following are the characteristics of step polymerization.
1) The monomers contain functional groups like –OH, -COOH, NH2, RCOOR1, halides etc.
2) The functionality of the monomer must be two or more than two. The monomers must be
dibasic acids, diols, diamines or triols etc.
3) The polymer is built up by a slow step wise condensation reaction of the functional
groups of the monomer.
4) The polymerization reaction is accompanied by the elimination of biproducts like HCl,
CH3OH, H2O etc.
5) The reaction is not exothermic.
6) The molecular weight of the polymer is not the sum of the molecular weights of the
monomers.
7) The polymers produced are living polymers containing functional groups at the end of the
chain.

8) It is not three step mechanism of initiation, propagation and termination.

9) The reactions are catalyzed by catalysts.
Examples:
1) Nylon 6,6
2) Polyester (Terylene (or) Dacron)
Difference between condensation and addition polymerization:

Condensation polymerisation Addition polymerisation
(1) It is also known as step growth (1) It is also known as chain growth
polymerization polymerization
(2) It takes place in monomers having (2) It takes place only in monomers
reactive functional groups having multiple bonds.
(3) It takes place with elimination of simple (3) It takes place without elimination of
molecule like H2O, NH3, HCl etc. simple molecule.
(4) Repeating units of monomers are (4) Repeating units & monomers are
different same
(5) The polymer is formed in gradual steps (5) Reaction is fast and polymer is
formed at once
(6) The molecular mass of polymer increases (6) There is very little change in the
throughout the reaction molecular mass throughout the reaction
(7) Product obtained may be (7) Products obtained are thermoplastic
thermosetting/thermoplastic
(8) E.g.: Bakelite, polyester, polyamides etc. (8) E.g: Polyethylene, PVC, polystyrene
Plastics:
Plastics are polymers characterized by the property of plasticity (permanent
deformation in structure on applying some stress/force). They can be moulded to desired
shape when subjected to heat and pressure in the presence of catalyst.
Plastics as engineering materials:

Advantages of plastics over other engineering materials
1. Low fabrication cost, low thermal & electrical conductivities, high resistance to
corrosion & solvents.
2. The stress – strain relationship of plastics is like that of metals.
3. Plastics reduce noise & vibration in machines.
4. Plastics are bad conductors of heat and are used to make handles for hot objects, most
plastics are inflammable.

5. Plastics are electrical insulators & find large scale use in the electrical industry.
6. Plastics are resistance to chemicals.
7. Plastics are clear & transparent so they can be given beautiful colours.
Types of Plastic: 1) Thermoplastics

2) Thermosetting plastics
Difference between Thermoplastic & Thermosetting resins:
Thermoplastic Resins Thermosetting Resins
1. These resins become soft on heating and 1. They do not soften on the heating and
rigid on cooling by regaining original become hard. On prolonged heating they
properties. These can be reshaped and used. decompose and cannot get back their
structure. Hence cannot be reshaped and
used.
2. The heating and cooling do not alter the 2. These resins are permanent setting resins.
chemical nature of these resins but involves
changes in physical nature.
3.They are formed by addition 3. They are formed by condensation

polymerization polymerization.
4. Small molecular weight compounds with 4. Large molecular weight compounds with
linear structures. three dimensional networks.
5. They consist of long chain linear polymer 5. Highly cross-linked structure strong
with weak secondary vandarwaal’s forces of covalent bonds are responsible for strength.
attraction in between them.
6. They soften on heating readily because 6.The bonds retain their strength on heating,
the secondary force of attraction between hence do not soften on heating
the individual chain can break easily by
heat, pressure or both
7. This plastic can be reclaimed from waste 7. Cannot be reclaimed from waste
8. They are soft, weak and less brittle 8. They are hard, strong and more brittle
9.These resins are usually soluble in organic 9. Due to strong bonds and cross links, they
solvents are insoluble in all organic solvents.
10. Curing by cooling 10. By applying heat and pressure
Ex: PE, PS, PVC, Teflon Ex: Bakelite, Polyester and silicones

Chemistry of some important thermoplastic & thermosetting resins:

(1) Polyvinyl chloride (PVC):
Preparation: The monomer used for the manufacture of PVC is vinyl chloride. Vinyl
chloride is prepared by treating acetylene with HCl at 60-800C and in presence of a metal
oxide catalyst. Polyvinyl chloride is produced by heating vinyl chloride in the presence of
benzyl peroxide or H2O2.
Properties:
 PVC is a colorless, non-inflammable and chemically inert powder
 It has specific gravity 1.33 and melting point 148oC
 Resistant to atmospheric conditions like O2, CO2 and moisture
 They are rigid and flexible
 It has resistance to light
Applications:
There are two kinds of PVC plastics
Rigid PVC (Unplasticized PVC):
 It is a chemically inert & non-inflammable powder having a high softening temperature
of 1480C.
 This PVC is used for making safety helmets, refrigerator components, tyres, cycle &
motorcycle mud guards.
Plasticized PVC:
 It is produced by mixing plasticizers like dibutyl phthalate with PVC resin uniformly.
 It is used for making raincoats, tablecloths, handbags, curtains & electrical insulators,
radio, T.V components. All PVC shoes for beach wear.
(2) Teflon (polytetrafluoro ethylene):

Preparation: Teflon is obtained by polymerization of tetrafluoro ethylene under pressure
in presence of benzoyl peroxide as catalyst.

Properties:
Teflon is also known as Fluon. Due to the presence of highly electronegative fluorine atoms,
Teflon has got:
 High melting point (350oC)
 The strong attractive force is responsible for high toughness & high chemical resistance
towards all chemicals except hot alkali metal & hot fluorine.
 High density 2.1-2.3gm/cc
 It is a very good electrical insulator
 It possesses very good abrasion resistance
Engineering applications:
 It is used in making seals & gaskets, which must withstand high temperatures.
 It is also used for insulation of electrical items and for making non-sticky surface coating,
particularly for cooking utensils.
 Teflon used as insulating material for motors, transformers, cables, wires, fitting etc.,
Some examples for Thermosetting Resins:

Bakelite (or) Phenol Formaldehyde Resin:
Bakelite is an important thermosetting resin named after the scientist Bakeland, who
synthesized this resin in the year 1909. The condensation reaction of phenol & formaldehyde
in the presence of acid or alkali catalyst and at proper temperature produces the phenol
formaldehyde resin or Bakelite resin.
Stage-I: The initial reaction of phenol & formaldehyde in presence of acid or alkali produces
o-hydroxy methyl phenol and p-hydroxy methyl phenol.
Stage-II: o-hydroxy methyl phenol undergoes self-condensation in presence of acid or alkali

and forms a linear polymeric chain called novolac.
Stage-III: On further heating, in the presence of hexamethylenetetramine both o-hydroxy

methyl phenol and p-hydroxy methyl phenol undergoes self-condensation and forms a 3D-
cross linked thermosetting polymer which is known as “Bakelite”.

Properties:
(1) Bakelite’s are hard, rigid and withstand very high temperatures.
(2) They have excellent heat and moisture resistance.
(3) They have good chemical resistance, resistance to acids, salts and many organic solvents,
but it is attached by alkalis due the presence of –OH group.
(4) They have good abrasion resistance.
(5) They have electrical insulation characteristics.
(6) It is a good anionic exchanging resin, exchange –OH group with another anion.
(7) Low molecular weight grades have excellent bonding strength and adhesive properties.
Engineering Applications:
(1) It is used for making electric insulator parts like switches, plugs, switchboards etc.
(2) For making moulded articles like telephone parts cabinet of radio and television.
(3) As an anion exchanger in water purification by ion exchange method in boilers.
(4) As an adhesive (binder) for grinding wheels etc.,
(5) In paints and varnishes.
(6) For making bearings used in propeller shafts, paper industry and rolling mills.
FIBERS:
Fibers are a class of materials that are continuous filaments or discrete elongated pieces.
They are crystalline, present in both plants & animals.
They are used for making textiles, ropes, utilities, strings etc.
These are of two types
(1) Natural Fibers
(2) Synthetic fibers
1. Natural fibers: Produced by plants, animals & geological materials.
a. Vegetable fibers: Cellulosic material
Ex: cotton, jute etc. used for making textiles, ropes, mats, paper, bags etc.
b. Wood fiber: The strength of a plant is due to the presence of wood fiber. Wood pulp is
used in making paper and wood fibers like jute are used for making bags.
c. Animal fibers: They are largely made of protein. E.g. Pure silk, wool, hair are animal
fibers. Spider silk is used for making special bullet proof jackets.
d. Mineral fibers: Asbestos is a typical example of mineral fiber. Mica & other minerals are
used as fibers.

2. Synthetic fibers: This type of fiber can be produced in large quantities and are cheaper
than some of the natural fibers like pure silk. Polyamide nylons, polyesters, PVC, phenol-
formaldehyde resin, polyethylene are often used for making textiles.
Nylon (Polyamide resin):

Nylon is a polyamide resin containing recurring amide groups in its structure
produced by copolymerization of di-amine with di-acid. Depending on the number of C
atoms in di-amine & di-acid there are different types of nylons like nylon 6,6, nylon 6,10 etc.,
where the first number indicates number of carbon atoms in di-amine & the second number
indicates the number of ‘C’ atoms in di-acid.
Nylon 6,6:
Preparation: It is prepared by condensation polymerization of adipic acid and
hexamethylene diamine in the absence of air.
Properties:
(1) They are translucent, whitish, horny, high melting polymer.
(2) They possess high temperature stability and good abrasion-resistance.
(3) They have good strength.
(4) They are insoluble in common organic solvents.
Applications:
(1) The major application is in the textile industry.
(2) Because of their high thermal & abrasion resistance nylons are used in mechanical
engineering applications like gears, bearings, machine parts where greater friction is
there.
(3) Flexible tubing’s for conveying petrol etc are made from nylons
(4) Nylons are used as electrical insulators.
(5) Nylon 6 is used for making tire cords.
(6) Nylons are used in automobile industry and telecommunication industry for making
radiator parts and coil formers respectively.
RUBBERS:
Those polymers which possess the property of elasticity is called rubber. Temporary
deformation in structure on applying some stress is more than 600e.u. When stress is applied
polymers, chains get partially aligned with respect to another, thereby causing
crystallization, temporary deformation which makes the polymer stiff. On releasing the
stress, the chains get reverted to their original coiled state. The elasticity of rubber is due to
its coiled helix structure.

Natural Rubber:
Natural Rubber is a high molecular weight hydrocarbon polymer represented by the
formula (C5H8)x. It is obtained from a milk emulsion called latex by tapping the bark of the
tree “Hevea brasiliensis.” The main composition of natural rubber is polyisoprene which is
in the form of long coiled chains. The isoprene units polymerise to form rubber. Isoprene in
natural rubber exits in two geometrical isomeric forms, cis and trans.
cis-polyisoprene is present in Natural rubber
trans-polyisoprene is present in Gutta percha rubber
VULCANIZATION:
Vulcanization is a chemical process used to enhance the properties of natural rubber, making
it more durable, elastic, and heat-resistant. The process involves adding sulfur or other
vulcanizing agents to rubber and then heating it to create cross-links between the polymer
chains.
- The rubber compound is heated, typically between 100°C to 140°C, in a mold or curing
press. During this process, sulfur forms cross-links between the rubber molecules, which
strengthens and stabilizes the material.
Applications
1. The major application of natural rubber is in the manufacture of tyres.
2. In heavy duty tyres, the major portion of the rubber used is natural rubber.
3. The tank linings in chemical plants where corrosive chemicals are stored are prepared
from rubber.
4. To reduce machine vibrations, rubber is used for sandwiching between two metal
surfaces.

5. Foam rubber is used for making cushions, matrices, padding etc. Toys and sports items
are manufactured from natural rubber.
6. Gutta percha is used for making submarine cables, golf ball covers, tissue or adhesive etc.
Conducting polymers:
Those polymers which conduct electricity are called conducting polymers. The
conduction of polymers is due to unsaturation or due to the presence of externally added
ingredients to them. Conducting polymers are classified into two types.
a) Intrinsic conducting polymers:
These are characterized by intensive conjugation of π-bonds in their structure. This is a
polymer whose back bones or associated groups consisting of delocalized electron pair or
residual charge, mostly increases their conductivity. The conduction process is due to the
overlapping of orbitals containing conjugated π-electrons, resulting in the formation of
valence bands as well as conduction bands separated by significant Fermi energy gap.
Electrical conductivity is due to thermal or photolytic activation of the electrons, which gives
them sufficient energy to cross the Fermi gap and cause conduction. Important commercially
produced intrinsic conducting polymers are polyacetylene, polythiophene, polyaniline.
Doped conducting polymers:

The conducting polymers having e-s in their backbone can easily be oxidized or reduced
because they possess low ionization potential and high electron affinities. Hence their conductance
can be increased by introducing a positive charge or negative charge on polymer backbone by
oxidation or reduction. This process is like semiconductor technology and is called doping. Doping
is again two types.
(1) Creating a positive site on the polymer backbone called p-doping.
(2) Creating a negative site on the polymer backbone called n-doping.
P-doping:
P-doping is carried out by oxidation process by the removal of an electron from conducting
polymer like polyacetylene with a Lewis acid or iodine. This is called oxidative doping.
During oxidation process the removal of π electrons from polymer back bone led to the
formation of a delocalized radical ion called polaron. The second oxidation of the polaron
leads to the formation of bipolaron, which are mobile because of delocalization. These
delocalized charge carriers (holes) are responsible for conductance when placed in electric
field.

N-doping:
N-doping is carried out by reduction process by the addition of an electron to conducting
polymer like polyacetylene with reducing agents like sodium napthalide Na(C10H8).
Formation of polaron, bipolaron takes place in two steps, which yields two negative charge
carriers on the polyacetylene chain. These delocalized charge carriers (electrons) are
responsible for conductance when placed in the electric field.
Applications of conducting polymers:

(1) The conducting polymers are used in rechargeable batteries, small in size (bottom size),
producing current density up to 50mA/cm2
(2) Conducting polymers are also used for making analytical sensors for PH, O2, NOx, SO2,
NH3 and glucose
(3) The conducting polymers are used for making ion exchangers. These membranes made of
conducting polymers show selective permeability for ions and gases hence they are used
for control release of drug.
(4) The conducting polymers are used for making electronic displays and optical fibres
(5) They are used for cancer chemotherapy
(6) The conducting polymers are applicable in photovoltaic devices, LED’s and data storage.
Biodegradable Polymers
Biodegradable polymers are defined as degradable polymers in which degradation is
caused by the action of naturally occurring microorganisms such as bacteria, fungi and algae.
During compositing they yield CO2, H2O, inorganic compounds and biomass without leaving
toxic residue
The biodegradable polymers may be naturally occurring or may be synthesized by
chemical means. In addition, feed stocks to synthesis these biodegradable polymers may
come from the processing of crops grown for the purpose or the byproducts of other crops,
along with chemical and biochemical processes.
Naturally occurring biodegradable polymers: A wide variety of naturally occurring

polymers are available, the fact that these substances were polymers was not known. In many
quarters this ignorance persists. The naturally biodegradable polymers are classified in to four
groups as given below.

Synthesized biodegradable polymers:

There are many polymers produced from derived from petrochemical or biological sources
that are biodegradable. There are a number of biodegradable synthetic resins that are:
1) Poly-lactic acid
2) Polyvinyl acetate
3) Polyvinyl alcohol
4) Polyamide esters
Polylactic acid or Polylactide (PLA):

 Polylactic acid is a biodegradable aliphatic thermoplastic polyester
 It is derived from renewable resources, such as corn starch (in the United States), tapioca
roots, chips or starch (mostly in Asia), or sugarcane (in the rest of the world).
 Lactic acid is obtained by the bacterial fermentation of sugarcane or from the starch
obtained from corn.
 Oligomerisation and catalytic dimerisation of lactic acid results in the formation of lactide
monomer
 Polylactic acid is obtained by the condensation polymerization of lactic acid in the
presence of acid or base catalyst.
Properties:
1. Due to the chiral nature of lactic acid, several distinct forms of polylactide exist: poly-L-
lactide (PLLA) is the product resulting from polymerization of L-lactide
2. PLLA has a crystallinity of around 37%, a glass transition temperature between 60-65°C, a
melting temperature between 173-178 °C
3. However, heat resistant PLA can withstand temperatures of 110°C
4. PLA is soluble in chlorinated solvents, hot benzene, tetrahydrofuran, and dioxane.
Applications
1. It is used in biomedical applications such as sutures, drug delivery devices and dialysis
media.
2. It is useful for producing loose-fill packaging, compost bags, food packaging, and
disposable tableware.
3. In the form of fibers and non-woven textiles, PLA also has many potential uses, for
example as disposable garments, awnings, feminine hygiene products, and diapers.
4. PLA is also used as a feedstock material in 3D printers such as Reprap and Makerbot.

ENGINEERING CHEMISTRY FUELS AND COMBUSTION
UNIT 4: ENERGY SOURCES

Introduction:
In recent years the dependency on energy by mankind has tremendously increased
because of increase in standard of living and rapid technological advances. The energy
needed today is derived from fossil fuels such as petroleum, coal and natural gas. Owing to
the growing demands of these fuels, a proper knowledge of various fuels, their utilization and
conservation is necessary.
Fuel:
A fuel can be defined as a combustible substance containing carbon as the major
constituent which can release a large amount of heat that can be used for domestic and
industrial needs. The main sources of fuel are coal and petroleum oils. For example, coal is
used in locomotives and as reducing agent in blast furnaces. Petrol is used in internal
combustion engines and for doing mechanical work.
Combustion is the process of chemical reaction between fuel and oxygen. During
combustion heat and products of combustion are released. The combustion process is an
exothermic chemical reaction.
Fuel Heat energy + Light + Combustion products
Heating value of a fuel is the amount of energy or heat released per unit mass during
combustion of that fuel. The main elements of combustion are carbon, hydrogen, sulphur,
oxygen and nitrogen.
Calorific value:The prime property of a fuel is its capacity to supply heat. Fuels
essentially consists of carbon, hydrogen, oxygen and some hydrocarbons and the heat that a
particular fuel can give is due to the oxidation of carbon and hydrogen. Normally when a
combustible substance burns the total heat depends upon the quantity of fuel burnt, its nature,
air supplied for combustion and certain other conditions governing the combustion. Further
the heat produced is different for different fuels and is termed as its calorific value.
Calorific value of a fuel may be defined as “the total quantity of heat liberated, when
a unit mass (or volume) of a fuel is burnt completely”. Or
“Calorific value is the amount of heat liberated by the complete combustion of a unit
weight of the fuel and is usually expressed as cal gm-1 or kcal gm-1 or B.Th.U. Or
The calorific value of a fuel can be defined as “the total quantity of heat liberated
when a unit mass of the fuel is completely burnt in air or oxygen”.

There are different units for measuring the quantity of heat. They are:
1. Calorie
2. Kilocalorie
3. British thermal unit (B.Th.U)
4. Centigrade heat unit (C.H.U)
1. Calorie:It is the amount of heat required to increase the temperature of 1 gram of water
through one degree centigrade.
2. Kilocalorie:This is the unit of heat in metric system and is defined as the quantity of heat
required to raise the temperature of one kilogram of water through one degree centigrade.
1 k.cal = 1000 cal

1 k.cal = 3.968 B.Th.U
3. British thermal unit (B.Th.U):This is the unit of heat in English system, it is defined as
“the quantity of heat required to increase the temperature of one pound of water through one
degree Fahrenheit.
1 B.Th.U = 252 cal = 0.252 k.cal
4. Centigrade heat unit (C.H.U):It is the quantity of heat required to raise the temperature
of one pound of water through one degree centigrade.
1 k.cal = 3.968 B.Th.U = 2.2 C.H.U
Inter conversion of various units of heat:
1 k.cal = 1000 cals = 3.968 B.Th.U = 2.2 C.H.U 1 B.Th.U = 252 cals
Units of calorific value:
For solid or liquid fuels: cal/g or k.cal/kg, B.Th.U/lb
For gaseous fuels: k.cal/cubic meter or k.cal/m3
B.Th.U/ft3 or B.Th.U/cubic feet
There are two types of calorific values of a fuel

1) Higher Calorific value (HCV) or Gross calorific value (GCV)
2) Lower Calorific value (LCV) or Net calorific value (NCV)
Higher or Gross calorific value(HCV):

It is defined as the total amount of heat produced when unit mass or unit volume of
fuel is completely burnt, and the products of combustion are allowed to cool to room
temperature. When a fuel containing hydrogen is burnt, the hydrogen present is converted to
steam. As the products of combustion are cooled to room temperature, the steam gets

condensed into water and the latent heat evolved. Thus, the latent heat of condensation of
steam, so liberated, is included in the gross calorific value.
Net calorific value or lower calorific value (LCV):

Whenever a fuel is subjected to combustion, the water vapour and moisture etc.,
escape along with the hot combustion gases and hence there is no chance for them to
condense. So the net or lower calorific value is defined as “the net heat produced, when unit
mass or unit volume of the fuel is burnt completely and the combustion products are allowed
to escape.
Relationship between HVC and LCV
LCV or NCV = HCV – Latent heat of water vapour formed
H2 + 1/2O2 H2O
2 gm 18 gm
1 gm 9 gm
Since 1 part by mass of hydrogen produces 9 parts by mass of water

Hence LCV = HCV – mass of hydrogen x 9 x latent heat of steam
Latent heat of steam is 587kcal/g.
Net calorific value = Gross calorific value – 9 x H/100 x 587
NCV = GCV – 0.09 x H x 587
Where H = % of hydrogen in the fuel
CLASSIFICATION OF FUELS:
Fuels can be classified into 2 types
a) On the basis of their occurrence
b) On the basis of physical state of aggregation
On the basis of occurrence:
1) Natural or primary fuels, which are found in nature such as e.g., wood, peat, coal,
petroleum, natural gas etc.
2). Artificial or secondary fuels are those which are prepared from the primary fuels. For
example, charcoal, coke, kerosene, diesel, petrol, coal gas, oil gas, producer gas, blast furnace
gas, etc.
On the basis of physical state of aggregation:

a) Solid fuels; b) Liquid fuels, and c) Gaseous fuel
Type of fuel Natural or primary Artificial or secondary

Solid Wood, peat, lignite, dung, Charcoal, coke etc.
bituminous coal and anthracite
coal

Liquid Crude oil Petrol, diesel and various other fractions

of petroleum
Gaseous Natural gas Coal gas, oil gas, bio gas, water gas etc.
Comparison of solid, liquid and gaseous fuels

S.NO Characteristic Solid fuels Liquid fuels Gaseous fuels
property of a
fuel
1 Example Coal Crude oil Coal gas
2 Cost Cheap Costlier than solid Costly
fuels
3 Storage Easy to store Closed containers Storage space required
should be used for is huge and should be
storing leak proof.
4 Risk towards Less More Very high, since these
fire hazards fuels are highly
inflammable
5 Combustion It is a slow Fast process Very rapid and
rate process efficient
6 Combustion Cannot be Cannot be controlled Controlled by
control controlled or stopped when regulating the supply
necessary of air
7 Handling cost High since labour Low, since the fuel Low, similar to liquid
is required in can be transported fuels, these can be
their storage & through pipes transported through
transport. pipes
8 Ash Ash is produced No problem of ash No problem of ash
and its disposal
also possess
problems
9 Smoke Produce smoke Clean, but liquids Smoke is not produced
invariably associated with high
carbon and aromatic
fuels produce smoke
10 Thermal Least High Highest
efficiency
11 Calorific value Least High Highest
12 Use in internal Cannot be used Can be used Can be used
combustion
engine
Characteristics of a good fuel:A good fuel should satisfy the following requirements:
 It should have a high calorific value per unit weight i.e. it should evolve a large amount of
heat when a unit weight of it is burnt under the conditions in which it is to be used as a
fuel.
 Its moisture content should be low, so that its heating value should be high.

 It should not produce harmful products like CO2, SO2, H2S and other poisonous gases on
burning since they pollute the atmosphere.
 A fuel should have low content of non-combustible matter in the form of ash or clinker.
The presence of non-combustible matter will enhance the cost of storage, handling and
disposal of the waste.
 In case of solid fuel, the fire should be controllable so that it can be started or stopped.
 It should be economical and easily available.
 It should not give any offensive odour.
 An ideal fuel should have moderate ignition temperature. Normally low ignition
temperature during storage and transport of fuel leads to fire hazards on the other hand,
fuel with high ignition temperature is safe for storage, handling and transport.
SOLID FUELS:
Coal:
Itis highly carbonaceous matter and is regarded as a fossil fuel produced from large
accumulations of vegetable debris and alternation of vegetable matter like plants etc. under
certain favorable conditions by the action of heat and pressure over millions of years. Coal is
mainly composed of carbon, oxygen, hydrogen and nitrogen.
Its formation can be explained by the following theories.
i) In-situ theory: This theory states that the coal formation took place at the same area where
vegetation grew and accumulated originally. The great purity of coal can be explainedon
the basis of this theory.
ii) Drift theory:According to this theory, the organic matter, vegetables, trees tec. when
uprooted due to climatic conditions are transported by rivers to lakes and get deposited in
the deeper parts of the soil.During a period of time, they undergo gradual decomposition
due to high temperature, pressure, absence of oxygen and presence of bacteria and
transformed into highly carbonaceous matter
Coal has been classified in several ways. The most common method of classification
is on the basis of rank. From the origin of coal it is clear the wood, after a long interval of
time and under certain conditions was converted into coal. The successive stages in the
transformation of vegetable matter into coal are wood, peat, lignite, bituminous coal and
anthracite coal.
Coal is classified based on the carbon content. The following is sequence of conversion.
Peat: Peat is regarded as the first stage in the transformation of wood into coal. Brown,
fibrous, jelly like mass. Un-economical fuel. Contains 80-90% of H2O. Composition C =
57%, H= 6%, O = 35%, ash 2.5 to 6%. Calorific value = 5400 kcal/kg.
Lignite:(Brown coal) soft, brown, colored, lowest rank coal and moisture content is 20 to
60%. Composition: C = 60%, O = 20%, Calorific value = 6,500 to 7,100 k.cal/kg

Bituminous coal:
Bituminous coal (common coal) Black to dark colored. This coal is largely used in
industries for making metallurgical coke, coal gas and for domestic heating. It has laminated
structure it is sub classified based on carbon content.
Composition is % of C = 78 to 90%, VM = 20 to 45%, CV = 8000 to 8500 kcal/kg.
Anthracite:
It is highest rank coal. These coals have very low volatile matter, ash & moisture.
This coal is very hard, dense and lustrous in appearance.
% of C = 98 %. CV = 8650 to 8700 k.cal/kg.
Fuel % of Calorific Value Main application

Carbon (k.cal/kg)
WOOD 50 4000-4500 Domestic fuels
PEAT 57 4125-5400 Used if high rank coal is deficient
LIGNITE 67 6500-7100 Used for steam generation in thermal power
plants and for the production of producer
gas
BITUMINOUS 83 8000-8500 Used in making coal gas and metallurgical
coke. Also used for steam generation in
thermal plants and for domestic heating.
ANTHRACITE 93 8650-8700 Used in household and for steam raising.
Also used in metallurgical purposes, where
no smoke and high local heat is desired.
Analysis of Coal:
The composition of coal varies widely and hence it is necessary to analyze the coal
samples so that types of coal can be selected for a particular industrial use. The following
methods of analysis can be utilized for the selection of coal.
1. Proximate analysis:
This analysis records moisture, volatile matter, ash and fixed carbon as percentages of
the original weight of the coal sample. Proximate analysis is of significance in
commercial classification and industrial utilization of coal.
2. Ultimate analysis:
This consists of determination of C, H, S, N and O. The ultimate analysis is essential
for calculating heat balances in any process for which coal is employed as a fuel.
1. Proximate analysis: It is a quantitative analysis of the following parameters.

1. Moisture
2. Volatile matter
3. Ash
4. Fixed carbon

Moisture:
About 1 gram of finely powdered air air-dried
dried coal sample is weighed in a crucible. The
crucible is placed inside an electric hot air oven, maintained at 105 to 1100C. The crucible is
air-oven,
allowed to remain in ovenen for 1 hour and then taken out, cooled in a desiccator
desiccat and weighed.
Loss in weight is reported as moisture.
Volatile Matter:
The dried sample is taken in a crucible and then covered with a lid and placed in an
ffle furnace, maintained at 9250C. The crucible is taken out of the oven
electric furnace or muffle
after 7 minutes of heating. The crucible is cooled first in air, then iinside
nside desiccator and
weighed again. Loss in weight is reported as volatile matter on percentage
percentage--basis.
Ash:
The residual coal sample taken in a crucible and then heated witho
without lid in a muffle
furnace at 750oC for half an hour. The crucible is then taken out, cooled first in air, then in
desiccator and weighed. Heatting,
ing, cooling and weighing is repeated, till a constant
const weight is
obtained. The residue is reported as ash on percentage
percentage-basis.
Fixed carbon:
After the determination of moisture, volatile matter and ash contents, the remaining
material is known as fixed carbon. It is determined indirectly by deducting the sum of the
percentages of moisture,, volatile matter and ash from 100
% of Fixed
ixed carbon = 1100 - % of (Moisture + Volatile matter + ash)
Significance of Proximate A
Analysis: Proximate analysis provides following valuable
information in assessing the quality of coal.
1. Moisture:
Moisture in coal evaporates during the burning of coal and it takes some of the
liberated heat in the form of latent heat of evaporation. Therefore, moisture lowers the
effective
ive calorific value of coal. More
Moreover, it quenches the fire in thee furnace, hence, lesser
thee moisture content, better the quality of coal as a fuel.

2. Volatile matter:
High volatile matter content means that a high proportion of fuel will distil over as
gas or vapour, a large proportion of which escapes un un-burnt, So, higher
gher volatile content in
i
coal is undesirable. A high volatile matter containing coal burns with a long flame, high
smoke and has low calorific value. Hence, lesser the volatile matter, better the rank of the
coal.
3.Ash: Ash is a useless, non--combustible
combustible matter, which reduces the calorific value of coal..
Hence, lower the ash content, better the quality of coal. The presence of ash also increases
transporting, handling and storage costs. It also involves additional cost in as
ash disposal.
4. Fixed carbon:: Higher the percentage of fixed carbon, great

greater is itss calorific value and
better is the quality of coal.
Ultimate analysis: This is the elemental analysis and often called as qualitative analysis
of coal. This analysis involves the determination of carbon and hydrogen, nitrogen, su
sulphur
and oxygen.
Carbon and Hydrogen:

About 1 to 2 grams of accurately weighed coal sample is bburnt
urnt in a current of oxygen
in a combustion apparatus. C and H of the coal are converted into CO2 and H2O respectively.
The gaseous products of combustion are absorbed respectively in KOH and CaCl2 tubes of
known weights. The increase in weights of these aare then determined.
C + O2 CO2
2KOH + CO2 K2CO3 + H2O
H2 + ½ O2 H2O
CaCl2 + 7 H2O  CaCl2.7H2O
% of Carbon = × × 100
% of Hydrogen = × × 100

Nitrogen:
About 1 gram of accurately weighed powdered coal is heated with concentrated
H2SO4 along with K2SO4 (catalyst) in a long long-necked
necked Kjeldahl’s flask. After the solution
becomes clear, i.e,, when whole nitrogen is converted into ammonium sulphate, it is treated
with excess of NaOHand and the liberated ammonia is distilled over and absorbed in a known
volume of standard acid solution. The unused acid is then determined by back titration with
standard
dard NaOH solution. From the volume of acid used by liberated ammonia, the percentage
of N2 in coal is calculated as follows:
K2SO4
× × .
% of N2 =
Sulphur:
Sulphur is determined from the washings obtained from the known mass of coal, used
in bomb calorimeter for determination of a calorific value. During this ddetermination, S is
converted into sulphates. The washings are treated with bbarium arium chloride solution, when
barium-sulphate
sulphate is precipitated. This precipitate is filtered, washed and heated to constant
weight.
O2 BaCl2 -
2-
S SO4 BaSO4 + 2Cl
×
% of Sulphur = × 100
×

Ash:
The residual coal is taken in a crucible and then heated without lid in a muffle furnace
0
at 750 C for ½ hour. The crucible is then taken out, cooled first in air, then in a desiccator
and weighed. Heating, cooling and weighing is repeated, till a constant weight is obtained.
The residue is reported as ash on percentage-basis.
Thus,
Oxygen:
It is determined indirectly by deducting the combined percentage of carbon,
hydrogen, nitrogen, sulphur and ash from 100.
% of Oxygen = 100 – % of (C + H + S + N + Ash)
Significance of Ultimate analysis:
 Carbon and Hydrogen: Greater the percentage of carbon and hydrogen, better is the
coal in quality and calorific value. However, hydrogen is mostly associated with the
volatile mater and hence, it affects the use to which the coal is put.
 Nitrogen: Nitrogen has no calorific value and hence, its presence in coal is undesirable.
Thus, a good quality coal should have very little nitrogen content.
 Sulphur: Sulphur, although contributes to the heating value of coal, yet on combustion
produces acids like SO2, SO3, which have harmful effects of corroding the
equipment’sand cause atmospheric pollution.
 Ash: Ash is a useless, non-combustible matter, which reduces the calorific value of coal.
Moreover, ash causes the hindrance to the flow of air and heat, thereby lowering the
temperature. Hence, lower the ash content, better the quality of coal. The presence of ash
also increases transporting, handling and storage costs.
 Oxygen:Oxygen content decreases the calorific value of coal. High oxygen-content coals
are characterized by high inherent moisture, low calorific value, and low coking power.
Moreover, oxygen is a combined form with hydrogen in coal and thus, hydrogen
available for combustion is lesser than actual one. An increase in 1% oxygen content
decreases the calorific value by about 1.7% and hence, oxygen is undesirable. Thus, a
good quality coal should have low percentage of oxygen.
LIQUID FUELS:
Petroleum or Crude oil
 The crude oil or petroleum also known as rock oil or mineral oil is a dark coloured liquid
found well deep in the earth.
 It is mainly composed of hydrocarbons which may be solids, liquids or gases.

 Some optical active compounds having S and N also present.

 On average the composition of petroleum is
C= 79.5-87.1% H= 11.5-14.8%
S = 0.1-3.5% N and O = 0.1-0.5%
Refining of Petroleum:
Crude oil obtained from the mines contains lot of soluble and insoluble impurities
which must be removed. Refining can be defined as the processby which crude oil is
separatedinto various useful fractions by fractional distillation and finally converted into
desired specific products. The industry where the refining of crude oil takes place is called oil
refinery.
Refining of petroleum is done in different stages:
a. Removal of solid impurities: The crude oil is a mixture of solid, liquid and gaseous
substances. This is allowed to stand undisturbed for some time, when the heavy solid
particles settle down and gases evaporate. The supernant liquid is then centrifuged where
in the solids get removed.
b. Removal of water (Cottrell’s process): The crude oil obtained from the earth’s crust is
in the form of stable emulsion of oil and brine. This mixture when passed between two
highly charged electrodes will destroy the emulsion films and the colloidal water droplets
coalesce into bigger drops and get separated out from the oil.
c. Removal of harmful impurities:In order to remove sulphur compounds in the crude oil,
it is treated with copper oxide. The sulphur compounds get converted to insoluble copper
sulphide, which can be removed by filtration.
d. Fractional distillation: Heating of crude oil around 4000C in an iron retort, produces hot
vapours which is allowed to pass through fractionating column. It is a tall cylindrical
tower containing several horizontal stainless trays at short distances and is provided with
small chimney covered with loose cap. As the vapours go up, they get cooled gradually
and fractional condensation takes place. Higher boiling fractions condenses first later the
lower boiling fractions

Name of Fraction Boiling Approx- composition

range in terms of
Uses
hydrocarbon ‘C’
atoms
(1) Uncondensed gas Below C1toC4 A domestic or industrial fuel.

300C
(2) Petroleum ether C5-C7 As a solvent.
300-700C
(3) Gasoline or C5-C9 As motor fuel, solvent, in dry
petrol 400-1200C cleaning
C9-C10
o
(4) Naphtha or 120-180 C As solvent, in dry cleaning
solvent spirit C10-C16
1800C- As an illuminant, Engine fuel
(5) Kerosene 2500C C10-C18
Diesel engine fuel
(6) Diesel oil 250-320 C o C17-C30
Gasoline by cracking
(7) Heavy oil on 320-400oC …….
refraction As lubricant
--- …….
(a) Lubricating oil As lubricant and in cosmetics
----- and ointments
(b) petroleum jelly
In candles, boot polishes
c) Paraffin wax
As lubricant
d) Greases
Used for making tar roads,
8) Residue (asphalt, waterproof roofing
petroleum coke)
Cracking of Petrol:
The quality and yield of petrol produced by the fractionation of petroleum is low.
Hence, the middle oil and heavy oil fractions are cracked to give petrol
Cracking is defined as the “decomposition of bigger hydrocarbon molecules into simpler, low
boiling hydrocarbons of low molecular weight”.
Cracking
Ex. C10H12C5H12 + C5H10
Decane Pentane Pentene
Advantages
 The yield of petrol is higher.
 The quality of petrol produced is better.
 No external fuel is necessary for cracking.
 Cracking can be easily controlled, so we can get desired products.
 Evolution of by-product gases can be minimized.

 Product contains very less quantity of undesirable sulphur content. So it is very useful.
Objectives:
A product from crude oil, gasoline has greater demand as motor fuel. But yield is only
upto 20%, more over fractional distillation have high content of sulphur. To overcome these
problems middle and heavy oil fractions are cracked to get petrol. The main objective of
cracking is to get desired products. Petrol made by cracking as good characteristics than
straight run petrol
Cracking is mainly two types:
1. Thermal cracking:In this process, heavier hydrocarbon molecules are converted into
lighter hydrocarbon molecules at high temperatures and pressures. Thermal cracking is
carried out in two ways. The cracked products are then separated by fractional distillation.
Generally, the yield is from 7 to 30%.
1) Liquid phase thermal cracking 2) Vapour phase thermal cracking
Liquid phase thermal cracking: In this method, cracking takes place at 4750C to 5300C and
at a high pressure of 100kg/cm2. The cracked components have octane number up to 70.
Vapour phase thermal cracking: It is conducted for oils having low boiling
temperatures.The cracking occurs at 600 to 6500C and comparatively at low pressure of 10 to
20 kg/cm2. It requires less time and the petrol obtained has better antiknock properties and
poor stability than the petrol obtained from liquid phase thermal cracking.
1. Catalytic Cracking:
In this type of cracking catalysts are used. The suitable catalysts used are Al2O3 and
Al2(SiO3). This process completes at lower temperatures and low pressures compared to
thermal cracking (300-450oC; 1-5kg/cm2 pressure). The petrol sample produced contains
higher content of aromatics, hence quality of petrol with better antiknock properties. The
petrol sample contains less percentage of sulphur, hence less corrosive.
Catalytic cracking may be:

1) Fixed bed catalytic cracking
2) Moving bed catalytic cracking
Moving bed or fluid bed catalytic cracking

Inthis process solid catalyst is made in the formof fine powder so that it moves freely in the
chamber like a fluid. Hence the process is known as fluid bed or moving bed catalytic
cracking.
Process:
1. The solid catalyst is finely powdered and mixed with oil and circulated as oil
vapourstothe reaction chamber (500 C)
2. In the reactor cracking of heavier to lighter hydrocarbons occurs

3. Near the top of the reactor, there is centrifugal separator, which allows only cracked oil
vapours to pass on to the fractionating column and retains the catalyst powder in the
reactor
4. The catalyst gradually becomes heavier due to coating with carbon and settles to
thebottom from where it is forced by an air blast to regenerator chamber (600o C)
5. In the regenerator, carbon is burnt and regenerator catalyst, then flows through a
standpipe or mixing with fresh batch of incoming cracking oil
6. The cracked oil vapours from the reaction chamber are passed through a fractionating
column, cooler and finally to stabilizer where the pure gasoline is obtained
Knocking
In an engine, "knocking" (also known as "pinging" or "detonation") refers to the occurrence
of uncontrolled combustion of the air-fuel mixture in the cylinder. Instead of the fuel burning
smoothly and evenly, it ignites prematurely or unevenly, causing shock waves and a
characteristic pinging or knocking sound. This phenomenon can lead to reduced engine
performance, increased wear and tear, and potentially severe engine damage if not addressed.
Knocking is often caused by factors such as low-octane fuel, incorrect ignition timing, high
engine temperatures, or an overly lean air-fuel mixture
Octane number:
1. The performance of gasoline in internal combustion has been rated based on octane
number
2. The higher the octane number, lower is knocking and better is its performance
3. The knocking is maximum for n-heptane and has lowest antiknock value and its octane
number is assigned as zero
4. Knocking is minimum for iso-octane (2,2,4-trimethyl pentane), has highest anti-knocking
value and its octane number is given as 100.
5. Octane number of gasoline is the percentage of iso-octane in the mixture of isooctane and
n-heptane which has same knocking as the gasoline itself
6. The higher the octane number, lower is knocking

7. The octane number of poor fuels can be raised by the addition of extremely poisonous
materials such as tetraethyl lead (C2H5)4Pb and diethyl-telluride (C2H4)2Te
8. The tendency of knocking is based on the chemical structure of hydrocarbons
n-paraffins >isoparaffins> Olefins > cycloparaffins >naphthalenes> aromatics
Decreasing order of knocking
(isooctane) octane number 100 (good fuel) octane number zero (bad fuel)
Diesel Knock:
Cetane Number:
1. The quality or rating of diesel is expressed by cetane number. Cetane is n- Hexadecane
(C16H34)
2. Diesel knock is due to post-ignition (delayed ignition) of fuel air mixture with the
application of heat and pressure but not by spark as in petrol I.C engine
3. n-Hexadecane has a short ignition lag as compared to any commercial diesel fuel. Its
cetane number is 100
4. α -methyl naphthalene has very long ignition lag as compared to any commercial diesel
oil. Its cetane number is taken as zero
5. Cetane Number is the percentage of n-hexadecane in a mixture of n- hexadecane and
α-methyl naphthalene which has the same ignition characteristics as that of the sample
under test.
6. The order of cetane number for the following is given as:
7. n-alkanes >naphthalenes> alkenes > branched alkanes > aromatics
8. n-alkanes have good anti-knock value and aromatics have least anti-knock value
2-methyl naphthalene n-hexadecane

Cetane number = 0 (bad fuel)Cetane number = 100 (good fuel)
Petrol knocking is defined as the rattling sound produced in petrol engine due to
pre-ignition of fuel air mixture
Diesel knocking is defined as the rattling sound produced in diesel engine due to
ignition lag of fuel air mixture
 Knocking is due to improper ignition of fuel –air mixture.

 Knocking decreases the efficiency of engine.
 Petrol Knock is maximum in open chain straight paraffins and least in aromatics
 For internal combustion engine a fuel is said to be a good fuel if it has least knocking

S. No Petrol Knocking Diesel Knocking

1 Petrol knocking is due to pre-ignition of Diesel knocking is due to post-
the fuel ignition (ignition–lag) of the fuel
2. Octane number is the rating of petrol Cetane number is the rating of
knock diesel knock
3 Straight chain hydrocarbons cause Aromatic hydrocarbons cause
maximum petrol knock whereas maximum diesel to knock
aromatics causes least knock whereas straight chain
hydrocarbons cause least knock
4 To improve anti-kock value TEL, and To improve antiknock value pre-
diethyl telluride are added ignition dopes like ethyl nitrite,
isoamyl nitrite and acetane peroxide
are added
Prevention of Knocking:To improve the antiknock value of the petrol sample,

Tetraethyl lead (TEL) and diethyl telluride [(C2H5)2Te] are added
Knocking can be prevented by using:

i) Good quality fuel with higher octane number
ii) By adding anti-knocking agents like tetraethyl lead, diethyl telluride etc.
iii) By retarding spark plug ignition
Leaded petrol:The variety of petrol in which tetra ethyl lead is added is called leaded
petrol.
Advantages: Usually, petrol with low octane number is not good quality petrol. It often
knocks (i.e., produces huge noise due to improper combustion). As a result of knocking,
petrol is wasted; the energy produced cannot be used in a proper way.
When tetraethyl lead is added, it prevents knocking, there by saves money and energy.
Usually, 1 to 1.5 ml of TEL is added per 1lit of petrol.
The mechanism of action is as follows:
First TEL will be transformed into finely divided particles of PbO which looks like a cloud.
This takes place in the cylinder. Then the PbO particles react with hydrocarbon peroxide
molecules formed, thus slowing down the oxidation process and prevent early detonation.
Thus, either knocking may be stopped or greatly reduced.
Disadvantages: Deposits of PbO are harmful to engine. So PbO must be eliminated from the
engine. For this purpose, little amount of ethylene dibromide is added to petrol. It converts

the harmful PbO to volatile PbBr2 and eliminated through exhaust. Presence of any sulphur
compounds
ds reduces the efficiency of TEL. However, lead bromide is harmful to environment
Synthetic petrol:
Because of increasing demand for petrol, the synthetic methods for preparation of petrol gain
more importance. The important processes commonly used for syn
synthesis
thesis of petrol are
1. Fischer-Tropsch’s method &
2. Bergius process.
Fischer-Tropsch’s method:
This method was developed
eloped by Franz Fischer & Hans T Tropsch
ropsch (German scientists).
The raw material is the hard coke which is converted into water gas (CO + H2) by passing
steam over red-hot coke.In general, the mechanism of the reactions can be represented as
Ni or Co
nCO + 2nH2CnH2n + nH2O
nCO + (2n + 1) H2 CnH2n+2 + nH2O
 Water gas (CO + H2) is mixed with hydrogen gas (H2) in the presence of catalyst
 Catalyst consists of mixture of 100 parts of Co, 5 parts of Th, 8 parts of MgO and 200
parts of Kieselguhr earth
 Water gas and hydrogen gas mixture is purified by passing through Fe2O3 and Fe2O3 +
Na2CO3
 Pressure is maintained to 55-25 atmosphere
 Passed
assed through a convertor where the catalyst and temperature are maintained at 200 200-
o
300 C.
 In the convertor polymerization takes place
 Hot gases are passed through a cooler where crude oil produced
 Crude oil is fractionated in a fractionating column and thee gasoline fraction is produced in
the top fraction
 The high boiling heavy oil is obtained at the bottom can be used for cracking to get more
gasoline

Gaseous fuels
Eg: Natural Gas
1. Natural gas is primary gaseous fuel. It is a fossil fuel
2. It is obtained from oil wells dug in the earth crust during mining of petroleum
3. It is mainly composed of methane and small quantities of ethane along with other
hydrocarbons
4. It is also known as methane gas or marsh gas as it majorly contains methane
5. Composition of Natural gas:
CH4 -88.5% C2H6 - 5.5% Propane - 3.7%
Butane - 1.8% H2, CO, CO2 -0.5%
6.Calorific value varies from 12000-14000 Kg/m3

7. It is used as a very good domestic fuel
8. It is used in the preparation of ammonia
9. It is used to prepare carbon black for rubber industry
10. It is used to prepare some synthetic proteins which are used as animal feed
Secondary Gaseous Fuels:

LPG (Liquified Petroleum Gas):
Liquefied Petroleum Gas (LPG) is primarily composed of hydrocarbons, specifically propane
(C3H8) and butane (C4H10), along with smaller amounts of other gases such as propylene,
butylene, and various trace gases. The exact composition can vary depending on the source
and processing of the gas, but typically it consists of approximately:
- Propane: 50-95%
- Butane: 5-50%
- Other Hydrocarbons (including propylene and butylene): Less than 5%
LPG is stored and transported in liquid form under pressure but is used as a gas, making it a
versatile fuel for heating, cooking, and in some cases, as an automotive fuel.
Characteristics
1. LPG is obtained as byproduct during refining of crude oil or from natural gas
2. It mainly contains n-butane, isobutane, butylene and propane
3. It has high calorific value: 27800 kcal/m3
4. It gives less CO and least un-burnt hydrocarbons. So, it causes least pollution
5. It gives moderate heat which is very useful for cooking
6. It tends to mix with air easily
7. Even though it is toxic, on combustion it gives no toxic gases
8. It neither gives ash or smoke content
9. It is cheaper than gasoline. Hence used as motor fuel
10. It is dangerous when leakage is there. It is highly knock resistant
11. LPG is used as domestic fuel and as a fuel in internal combustion engines
12. It is used as fuel in some industries

 LPG can be compressed under pressure in containers and sold under the trade name like
Indane gas, Bharath gas etc.
 Traces of smelling organic sulphides (mercaptons)are added to LPG for safety measures
(to give warning of gas leakage)
CNG (Compressed Natural Gas):

1. Natural gas mainly contains CH4. CNG is made by compressing natural gas to less than
1% of the volume it occupies at STP
2. It is stored in a cylinder made of steel at a pressure of 200-248Kg/cm3
3. It is odourless, nontoxic gaseous mixture
4. Composition of CNG is CH4 (90%), other constituents are ethane, propane and gases like
N2, CO etc.
5. Calorific value of CNG is 900KJ/mole
Advantages:
1. Due to higher temperature of ignition, CNG is better fuel than petrol and diesel
2. Operating cost is less
3. It releases least pollutants like CO and unburnt hydrocarbons
4. It mixes with air easily and undergoes regular combustion
5. No anti-knocking agent is required as it has high octane number
6. It is used as fuel in automobiles like cars, trucks, buses etc.
7. It is also used as fuel for locomotive diesel generators to generate electricity that drive the
motors of train

Composite Materials:
A composite material (also called a composition material or shortened to composite, which is
the common name) is a material made from two or more constituent materials with
significantly different physical or chemical properties that, when combined, produce a
material with characteristics different from the individual components.
Fiber Reinforced Plastics (FRP):

 Combination of plastic material & solid fillers give hard plastic with mechanical strength
& impact resistant is known as reinforced plastic.
 The fiber polymers with solid/fillers to impart mechanical strength & hardness without
losing plasticity are known as fiber reinforced plastics (FRP).
 Fillers like carborandum, quartz & mica – impart hardness & strength.
 Barium salt impervious to x-rays.
 Asbestos provides heat & corrosion resistant for FRP.
Nature of polymers used for FRP:
Composition of FRP – 50% of the mouldable mixture contains fillers.
 The addition of carbon black to natural rubber increases the 40% strength of rubber &
used in the manufacture of tyres.
 China clay improves the insulation property of PVC, Teflon.
 When CaCO3 is added to PVC, then they are used for insulation of tubing, seat covers,
wires & cables.
 Asbestos filled FRP → for electrical appliances.
 FRP has good shock & thermal resistances, mouldability, dimensional stability &
reparability.

Applications
 Fiber reinforced plastics find extensive use in space crafts, aeroplanes, boat nulls, acid
storage tanks, motor cars and building materials.
 Melamine FRP is used for insulation & making baskets
Advantages of FRP
(a) Low efficient of thermal expansion

(b) High dimensional stability
(c) Low cost of production
(d) Good tensile strength
(e) Low dielectric constant
(f) Noninflammable & non-corrode and chemical resistance
Glass Reinforced Plastics:

Glass reinforced plastic (shortened as GRP) is made of synthetic resin as main basic material
and glass fiber or other product as reinforced material, processed into a solid material by
molding and setting
Fiberglass is a common type of fiber reinforced plastic using glass fiber. The fibers may be
randomly arranged, flattened into a sheet (called a chopped strand mat), or woven into
a fabric. The plastic matrix may be a thermoset polymer matrix — most often based
on thermosetting polymers such as epoxy, polyester resin or vinyl ester or a thermoplastic.
Applications:
1. Fiberglass is an immensely versatile material due to its light weight, inherent strength,
weather-resistant finish and variety of surface textures
2. During World War II, fiberglass was developed as a replacement for the molded
plywood used in aircraft radomes (fiberglass being transparent to microwaves).
3. Fiberglass is also used in the telecommunication1 industry for shrouding antennas ,
due to its RF permeability and low signal attenuation properties.
4. Because of fiberglass's light weight and durability, it is often used in protective
equipment such as helmets. Many sports use fiberglass protective gear, such as
goaltenders' and catchers' masks.
5. Storage tanks can be made of fiberglass with capacities up to about 300 tones.
6. Glass-reinforced plastics are also used to produce house building components such as
roofing laminate, door surrounds, over-door canopies, window canopies and dormers,
chimneys, coping systems, and heads with keystones and sills
7. In rod pumping applications, fiberglass rods are often used for their high tensile
strength to weight ratio. Fiberglass rods provide an advantage over steel rods because
they stretch more elastically (lower young modulus) than steel for a given weight,
8. GRP and GRE pipe can be used in a variety of above- and below-ground systems.

Carbon Reinforced Fiber:

Carbon fiber reinforced polymer or carbon fiber reinforced plastic, or carbon fiber reinforced
thermoplastic, is an extremely strong and light fiber-reinforced plastic which contains carbon
fibers.
One method of producing CFRP parts is by layering sheets of carbon fiber cloth into a mold
in the shape of the final product. The alignment and weave of the cloth fibers is chosen to
optimize the strength and stiffness properties of the resulting material. The mold is then filled
with epoxy and is heated, or air cured.
Carbon Fiber Reinforced Plastics are very hard to machine and cause significant tool wear.
The tool wear in CFRP machining is dependent on the fiber orientation and machining
condition of the cutting process. To reduce tool wear various types of coated tools are used in
machining CFRP and CFRP-metal stack.
Applications
Aerospace engineering
CFRP is widely used in micro air vehicles (MAVs) because of its high strength to weight
ratio.
Automotive engineering
Many supercars over the past few decades have incorporated CFRP extensively in their
manufacture, using it for their monocoque chassis as well as other components.
Civil engineering
CFRP has become a notable material in structural engineering applications
Carbon-fiber microelectrodes
Carbon fibers are used for fabrication of carbon-fiber microelectrodes.
Carbon-fiber microelectrodes are used either in amperometry or fast-scan cyclic voltammetry
for detection of biochemical signaling.
Sports goods
CFRP is now widely used in sports equipment such as in squash, tennis, and badminton
racquets, sport kite spars, high-quality arrow shafts, hockey sticks, fishing rods, surfboards,
high end swim fins, and rowing shells.

SMART MATERIALS
Smart materials are materials designed to respond dynamically to changes in their
environment. They can alter their properties in reaction to external stimuli like temperature,
light, heat, electric fields, or mechanical stress. All these changes are reversible, as the
materials return to their original states once the external stimuli expire.
Key Characteristics of Smart materials:
1. Responsiveness: Smart materials change their properties or behavior in response to

environmental stimuli. For instance, shape memory alloys and self-healing materials can
return to their original shape when heated.
2. Adaptability: They can adjust to varying conditions, which allows them to perform
specific functions or improve performance in changing environments.
3. Functional Integration: Smart materials often combine multiple functionalities into a

single material, such as sensing and actuation, which enables more complex and efficient
systems.
Classification of Smart materials:
On the Basis of External stimulus smart materials are classified into Three types.
1. Thermoresponsive materials: These are the materials that exhibit a change in their
properties in response to temperature changes. These materials can alter their physical
state, mechanical properties, or chemical behavior when subjected to temperature
variations, Ex: Thermoresponsive Polymers, Thermoresponsive Hydrogels,
Thermoresponsive Elastomers, Thermal Shape memory compounds etc.
2. Light responsive materials: Light-responsive materials are materials that change their
properties or behavior in response to light exposure. These materials are often referred to
as photo-responsive or photonic materials and are used in a wide range of applications
including sensors, switches, and adaptive devices. The response to light can be based on
various mechanisms, such as changes in color, phase, or shape, and can be triggered by
different types of light, including visible, ultraviolet (UV), and infrared (IR) light, Ex:
Photochromic Materials, Photothermal Materials, Photoelectric Materials etc.
3. Stimulous - Responsive materials: Stimulus-responsive materials are a class of smart

materials that react to external stimuli by changing their properties or behavior. These
stimuli can include physical, chemical, or environmental factors. The ability of these
materials to respond to stimuli makes them useful in a wide range of applications, from
medical devices to environmental sensors, Ex: Electro-Responsive Materials, Magneto-
Responsive Materials, Chemical-Responsive Materials, Piezo- Electric Materials.

Polyacrylamides (PAM):
These compounds are well known for their thermoresponsiveness. The repeating unit in
polyacrylamide is derived from acrylamide.
NH2
H
N
O O
acrylamide Polyacrylamide
Polyacrylamide is synthesized through the addition polymerization of acrylamide monomers

in presence of radical initiator. The polymer backbone consists of repeating acrylamide units
connected by amide linkages.
Thermoresponsive behavior:
Polyacrylamides are not inherently thermoresponsive but can be engineered to exhibit

thermoresponsive properties, especially in the form of hydrogels or through functionalization,
by incorporating specific chemical groups or creating cross-linked networks, polyacrylamides
can be modified for applications that require responsiveness to temperature changes.
PAM Hydrogels: These hydrogels can swell or shrink in response to temperature changes.
This behavior can be enhanced by incorporating specific functional groups or cross-linkers
into the polymer network.
 Lower Critical Solution Temperature (LCST): By modifying polyacrylamide with

temperature-sensitive groups, such as thermosensitive co-monomers or hydrophobic
moieties, PAM hydrogels can exhibit LCST behavior. Below the LCST, the hydrogel
remains swollen due to its hydrophilic nature. Above the LCST, the hydrogel collapses or
shrinks due to reduced hydrophilicity and increased hydrophobic interactions.
 Cross-Linking: Cross-linking polyacrylamide can influence its thermoresponsive
properties. Cross-linked networks can maintain their structural integrity while undergoing
swelling and deswelling in response to temperature changes.
Applications:
 Drug Delivery: Thermoresponsive polyacrylamide hydrogels can be used for controlled

drug release. The hydrogels can be designed to release drugs in response to temperature
changes, which is useful for targeted delivery or stimuli-responsive therapies.
 Tissue Engineering: Polyacrylamide-based hydrogels are used in tissue engineering as
scaffolds that can support cell growth and adapt to physiological temperature changes.
 Water Treatment: Polyacrylamide hydrogels can be used in water treatment processes
due to their high-water absorption capacity and ability to undergo swelling and shrinking.
 Sensors: Thermoresponsive PAM hydrogels can be used in temperature sensors and
actuators that respond to environmental temperature changes.

Polyvinyl Amides (PAM):
Polyvinyl amide is derived from vinyl amide monomers. The polymer is typically produced
by the polymerization of N-vinylformamide or N-vinylacetamide. The repeating unit in
polyvinyl amides is characterized by an amide group attached to a vinyl group.
NH
NH
n
O R
R O
R =H, N-vinylformamide. R =H, Poly vinylformamide.
R =CH3, N-vinylacetamide. R =CH3, Poly vinylacetamide.
 Thermoresponsiveness:
Polyvinyl amides exhibit thermoresponsive behavior due to the presence of amide groups,
which can interact with water and undergo phase transitions. The thermoresponsiveness is
often related to:
Hydrophilic-Hydrophobic Balance: The balance between hydrophilic and hydrophobic

interactions in polyvinyl amides influences their thermoresponsive properties.
Phase Transition: Like polyacrylamides, polyvinyl amides can be designed to exhibit LCST
behavior where they change their solubility or phase state in response to temperature changes.
Applications:
 Biomedical: Used in drug delivery systems and as components in tissue engineering due to
their biocompatibility and ability to respond to physiological conditions.
 Sensors: Employed in temperature sensors and actuators due to their ability to change
properties with temperature fluctuations.
 Coatings: Used in smart coatings that can alter their properties in response to
environmental temperature changes.
Shape memory materials:
Shape memory materials are a class of smart materials that can "remember" and return to a
predefined shape after being deformed. They can be triggered to revert to their original shape
by applying a specific stimulus, such as heat, light, or an electric field. Shape memory
materials find their applications in various fields like Aerospace, Automotive Industry, Civil
Engineering, Robotics, Textiles and Microelectronics.

Diagramatic Representation of Shape memory
Types of Shape Memory Materials:
1. Shape Memory Alloys (SMAs):
SMAs exhibit a phase transition between two different crystalline structures (martensite and
austenite) at specific temperatures. When heated above a certain temperature, SMAs revert to
their original shape due to this phase change.
Common Examples: Nickel-Titanium alloys (Nitinol), Copper-Aluminum-Nickel alloys.
2. Shape Memory Polymers (SMPs):
SMPs, like Poly L-lactic acid (PLLA) or polystyrene, have a temporary shape that can be
changed by applying a specific stimulus such as temperature. They generally work by
changing their physical state from glassy (hard) to rubbery (soft) and back, which allows them
to recover their original shape.
Applications of Shape Memory Polymers:
 Medical Devices
Stents and Implants: SMPs can be used in stents and implants that expand or change shape
at body temperature, facilitating minimally invasive procedures and enhancing patient
outcomes.
Surgical Tools: Surgical instruments made from SMPs can adapt their shape to perform
specific tasks or to navigate complex anatomical structures.
Wound Dressings: SMP-based dressings can conform to wounds and change shape to
provide better coverage or enhanced healing conditions.

 Aerospace
Deployable Structures: In spacecraft, SMPs are used in deployable components such as

antennas and solar panels that fold during launch and expand once in space.
 Robotics
Soft Robotics: SMPs are utilized in soft robotic components that can change shape to
handle various tasks or adapt to different environments, such as grippers or actuators.
 Energy
Thermal Energy Storage: SMPs can be used in systems designed to store and release
thermal energy, taking advantage of their phase transition properties for energy management.
 Textiles and Clothing
Adaptive Fabrics: Clothing made from SMPs can adjust to the wearer’s body shape or
environmental conditions (like temperature or humidity), improving comfort and fit.
Poly L-lactic acid (PLLA):
Poly L-lactic acid (PLLA) is a synthetic polymer derived from lactic acid, an organic acid that
is found naturally in many biological processes. The structure of PLLA is characterized by the
repeating units of L-lactic acid. In PLLA, the L-lactic acid monomers are linked together
through ester bonds to form long chains. The polymer backbone consists of repeating ester
linkages between the carboxyl group of one monomer and the hydroxyl group of the next.
Structure of Poly L-lactic acid (PLLA)
Poly L-lactic acid (PLLA) as Shape Memory Polymer:
PLLA can "memorize" its original shape after being deformed. This is achieved through a
process of programming the polymer by heating it above its glass transition temperature (Tg)
and then cooling it while in a deformed state. When reheated, the PLLA can revert to its
original shape. The shape memory behavior of PLLA is highly dependent on temperature. It
typically requires heating to temperatures above its Tg to switch back to its original shape.
The specific temperature at which this transition occurs can be tailored by modifying the
polymer's molecular weight and other properties.

Advantages:
PLLA is used in a range of applications due to its shape memory properties.
 In the biomedical field, it can be used for self-healing devices, stents, and sutures.
 In industrial applications, it is employed in manufacturing processes where temporary
shapes are required
 One of PLLA's advantages is its biodegradability. This makes it a suitable material for
applications where environmental impact is a concern, such as in medical devices and
environmentally friendly packaging.
Disadvantages:
 PLLA can be more expensive than some other polymers, so cost considerations are
important for large-scale applications.
 The processing conditions for PLLA, including temperature and cooling rates, must be
carefully controlled to achieve the desired shape memory effects.
LUBRICANTS
Lubricants are substances used to reduce friction between surfaces that are in contact with
each other, such as engines, gears, and moving parts. They help to:
1. Reduce wear and tear

2. Prevent overheating
3. Improve efficiency
4. Protect against corrosion
Classification of Lubricants:
Lubricants can be classified based on several criteria, such as their origin, state, and
application. Here's a detailed classification:
1. Based on Origin
A. Mineral Lubricants
- Derived from crude oil.
- Types: Paraffinic, Naphthenic, Aromatic.
B. Synthetic Lubricants
- Chemically engineered.
- Types: Polyalphaolefins (PAO), Esters, Polyalkylene glycols (PAG), Silicones.
C. Biodegradable/Bio-based Lubricants
- Made from vegetable oils or animal fats.
- Environmentally friendly.
2. Based on State
A. Liquid Lubricants
- Oils (Mineral, Synthetic, Vegetable).

B. Semi-Solid Lubricants
- Greases (Thickened oils, usually with soaps).
C. Solid Lubricants
- Graphite, Molybdenum disulfide, PTFE (Teflon).
D. Gaseous Lubricants
- Air, Inert gases.
3. Based on Application
A. Automotive Lubricants
- Engine oils, Transmission fluids, Gear oils.
B. Industrial Lubricants
- Hydraulic fluids, Compressor oils, Turbine oils, Metalworking fluids.
C. Marine Lubricants
- Cylinder oils, System oils, Stern tube oils.
D. Aerospace Lubricants
- High-temperature and high-pressure resistant lubricants.
4. Based on Viscosity Grade

A. Single-grade Lubricants
- Defined by a single viscosity rating.
B. Multi-grade Lubricants
- Designed to perform well over a range of temperatures (e.g., 10W-30).
5. Based on Functionality
A. Lubricating Oils
- Primary function: Reduce friction and wear.
B. Hydraulic Oils
- Transmit power to hydraulic systems.
C. Gear Oils
- Provide lubrication and cooling in gear systems.
D. Cutting Fluids
- Cool and lubricate cutting tools during machining.
E. Compressor Oils
- Lubricate and cool air compressors.
6. Based on Additives
A. Detergent Oils
- Contain detergents to keep engines clean.
B. Anti-wear Oils
- Contain additives like zinc dialkyldithiophosphate (ZDDP) to prevent wear.
C. Extreme Pressure (EP) Oils
- Contain sulfur-phosphorus additives to prevent metal-to-metal contact under high
pressure.
D. Rust and Oxidation Inhibited Oils
- Contain inhibitors to prevent rust and oxidation.

This classification helps in selecting the right lubricant for specific applications, ensuring
optimal performance and longevity of machinery and components.
Characteristics of a good lubricant:
A good lubricant possesses several key characteristics to ensure effective performance and
longevity of mechanical systems. These characteristics ensure that the lubricant can
effectively protect and enhance the performance of mechanical systems, extending their
lifespan and reducing maintenance needs.
Here are some of the main characteristics:
1. Viscosity: The lubricant should have the appropriate viscosity for the application,
maintaining a balance between being thick enough to provide a protective film and thin
enough to flow easily.
2. Thermal Stability: It should resist breaking down or oxidizing at high temperatures,
maintaining its properties under a wide range of temperatures.
3. Oxidation Resistance: A good lubricant should resist oxidation, which can lead to sludge
and varnish formation, degrading performance.
4. Corrosion Protection: It should protect metal surfaces from corrosion and rust, which can
cause wear and damage.
5. Water Resistance: The lubricant should be able to repel water and prevent it from
reaching metal surfaces, which can cause rust and reduce lubrication.
6. Load Carrying Capacity: It should have the ability to withstand high loads and pressures
without breaking down or losing its lubricating properties.
7. Friction Reduction: A good lubricant should minimize friction between moving parts,
reducing wear and improving efficiency.
8. Adhesion: It should adhere well to surfaces without being easily wiped or washed away,
ensuring consistent lubrication.
9. Chemical Stability: The lubricant should remain chemically stable and not react adversely
to the materials it contacts.
10. Environmental Compatibility: Ideally, it should be non-toxic and environmentally
friendly, posing minimal risk to humans and the environment.
11. Compatibility with Materials: It should not cause degradation or swelling of seals,
gaskets, or other materials in contact with it.

Properties of lubricants:
Lubricants have several key properties that determine their performance and suitability for
various applications. Here are some of the main properties of lubricants:
1. Viscosity: Viscosity is a measure of the internal resistance of a liquid during its flow. It is
expressed in centi poise.
A good lubricant oil must have moderate viscosity.
2. Flash point: It is the lowest temperature at which the oil gives off enough vapour to ignite
for a moment, when a small flame is brought near it.
3. Fire point: It is the lowest temperature at which the vapour of the oil burns continuously
for at least 5 seconds, when a small flame is brought near it.
Generally, the fire point is 5 to 40oC higher than flash point
Significance
A knowledge of flash and fire point is useful in providing protection against fire hazards
during transport and storage.
4. Pour point: the temperature at which the oil ceases to flow or pour is called its pour point.
5. Cloud point: when an oil is cooled slowly, the temperature at which the oil becomes
cloudy in appearance is called its cloud point.
Significance
A good lubricant must have low cloud point and pour point.

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MRCETCAMPUS

MALLA REDDY COLLEGE OF ENGINEERING ANDTECHNOLOGY

Unit –I Water and its treatment: (8 hours)

UNIT–II Battery Chemistry & Corrosion: (8 hours)

UNIT-III: Polymeric materials: (8 hours)

Malla Reddy College of Engineering and Technology www.mrcet.ac.in

UNIT-IV: Energy Sources: (8 hours)

Unit- V Engineering Materials: (8 hours)

Suggested Text Books:

The students will be able

Malla Reddy College of Engineering and Technology www.mrcet.ac.in

S. No. Contents Page No.

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

UNIT-IV: Energy Sources

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD)

0-70mg/liter Soft water

70-150mg/liter Moderate hard water

150-300mg/liter Hard water

300mg/liter and above Very hard water

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 1

Name of the salt Molecular weight

Expression of hardness – Units

DEPARTMENT OF HUMANITIES & SCIENCES ©MRCET (EAMCET CODE: MLRD) 2

1 L = 1 Kg = 1000 g = 1000 x 1000 mg = 106 mg.

Milliequivalents per litre : - No of milliequivalents of hardness present per liter of water.

Relation between various units of hardness:

1 ppm = 1mg /L = 0.10Fr = 0.07 0Cl = 0.02 meq /L

Total hardness of the sample water=121ppm=121mg/L

Ca(HCO3)2 → CaCO3 + H2O + CO2

Mg(HCO3)2 → Mg(OH)2 + 2CO2

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1 Mg(HCO3)2 14.6 100/146 14.6x100/146

2 NaCl 11.7 ------ -----------------

3 MgCl2 48 100/95 48x100/95 =50

4 CaSO4 13.6 100/136 13.6x100/136

5 Ca(HCO3)2 32.4 100/162 32.4x100/162

Temporary hardness = Mg(HCO3)2+ Ca(HCO3)2

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1 Mg(HCO3)2 25.6 100/146 25.6x100/146=17.5

2 Ca(HCO3)2 15.6 100/162 15.6x100/162 =9.6

3 NaCl 16.7 ------------- --------------

4 CaSO4 6.5 100/136 6.5x100/136 =4.77

5 MgSO4 5.4 100/120 5.4x100/120 =4.5

Temporary hardness = Mg (HCO3)2 + Ca (HCO3)2

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Disinfection of surface water / Removal of micro-organisms in water:

Break point chlorination:

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Advantages of breakpoint chlorination:

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Scale and Sludge formation in boilers:

Sludges and Scales in boilers

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Causes of scale formation:

Ca(HCO3)2 → CaCO3 + H2O + CO2

CaCO3 +H2O → Ca(OH)2 + CO2

b. Decomposition of calcium sulphate:

MgCl2 + 2H2O →Mg(OH)2 + 2HCl